CN101548204B - Pressure-sensitive adhesive for optical films - Google Patents

Pressure-sensitive adhesive for optical films Download PDF

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Publication number
CN101548204B
CN101548204B CN2007800444867A CN200780044486A CN101548204B CN 101548204 B CN101548204 B CN 101548204B CN 2007800444867 A CN2007800444867 A CN 2007800444867A CN 200780044486 A CN200780044486 A CN 200780044486A CN 101548204 B CN101548204 B CN 101548204B
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Prior art keywords
acrylic acid
acid series
triblock copolymer
series triblock
sensitive adhesive
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CN2007800444867A
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CN101548204A (en
Inventor
森下义弘
浜田健一
国宗哲也
石浦一成
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Kuraray Co Ltd
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Kuraray Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/24—Graft or block copolymers according to groups C08L51/00, C08L53/00 or C08L55/02; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
    • Y10T428/2852—Adhesive compositions
    • Y10T428/2878—Adhesive compositions including addition polymer from unsaturated monomer
    • Y10T428/2891—Adhesive compositions including addition polymer from unsaturated monomer including addition polymer from alpha-beta unsaturated carboxylic acid [e.g., acrylic acid, methacrylic acid, etc.] Or derivative thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31786—Of polyester [e.g., alkyd, etc.]
    • Y10T428/31797—Next to addition polymer from unsaturated monomers

Abstract

The present invention provides a pressure-sensitive adhesive for optical films which exhibits high cohesive force, and excellent reworkability, pressure-sensitive adhesion characteristics, heat resistance and endurance in spite of its dispensing with chemical crosslinking. [MEANS FOR SOLVING PROBLEMS] A pressure-sensitive adhesive for optical films which contains at least 60% by mass (based on the whole solid matter) of an acrylic triblock copolymer (I) represented by the general formula: A1-B-A2 in which alkyl methacrylate polymer blocks (A1) and (A2) having Tg of 100 DEG C or above are bonded to an acryl acrylate polymer block (B) having Tg of -20 DEG C or below and which has a block (B) content of 50 to 95% by mass, Mw of 50,000 to 300,000 and a molecular weight distribution of 1.0 to 1.5. It is preferable to use as the acrylic triblock copolymer (I) a blend which comprises an acrylic triblock copolymer (Ia) having Mw of 50,000 or above but below 100,000 and an acrylic triblock copolymer (Ib) having Mw of 100,000 to 300,000 at a (Ia):(Ib) mass ratio of 45:55 to 75:25.

Description

Pressure-sensitive adhesive for optical films
Technical field
The present invention relates to be suitable for polarization plates, phase retardation film (phasic difference Off イ Le system), other blooming pasted on the adherend such as liquid crystal panel, or on blooming, paste the pressure-sensitive adhesive for optical films of diaphragm.In addition, the present invention relates to have the adhesive optical film and the adhesive optical film diaphragm of the adhesive phase that forms by above-mentioned pressure-sensitive adhesive for optical films, and use above-mentioned adhesive optical film and/or the adhesive optical film image display device of diaphragm.
Background technology
Using bonding agent; bloomings such as polarization plates, phase retardation film are pasted on liquid crystal panel etc.; or when pasting diaphragm on the blooming; produce fold, bubble, foreign matter etc. enter or the situation about departing from etc. of paste position under; sometimes peel off the blooming of temporary transient stickup or diaphragm, carry out paste operation again once more, or after peeling off blooming, reclaim expensive liquid crystal panel recycling.Thus; for blooming being pasted on the adherend such as liquid crystal panel or paste the pressure-sensitive adhesive for optical films that uses in the diaphragm on blooming, adhesive-free re-workability residual, that can peel off, can paste once more with suitable peel strength is necessary.
Further, for pressure-sensitive adhesive for optical films,, do not have foaming or be necessary from the high permanance that adherend is peeled off even be exposed under heating, the humid tropical condition.
As pressure-sensitive adhesive for optical films, having proposed (1) contains and has glass transition temperature (Tg) is more than 50 ℃ and molecular weight be 500～1,000,000 high-tg polymer segment and Tg than whole molecular weight of its low low Tg polymer segment more than 70 ℃ is the polarization plates of 400,000～2,000,000 graft copolymer or segmented copolymer or polarizer with bonding agent (with reference to patent documentation 1), (2) with respect to acrylic acid series polymeric compounds 100 weight portions of weight-average molecular weight more than 1,000,000, with the ratio of 1～40 weight portion contain glass transition temperature for below-50 ℃ and weight-average molecular weight be the pressure-sensitive adhesive for optical films (with reference to citing document 2) of 800～50,000 acrylic oligomers, (3) contain the pressure-sensitive adhesive for optical films of acrylic oligomers, described acrylic oligomers contains with weight-average molecular weight and is preferably acrylic acid series polymeric compounds more than 1,000,000 as principal ingredient, have the segmented copolymer (with reference to citing document 3) of independent glass transition temperature for the polymer blocks below-5 ℃.
But in the patent documentation 1, in fact as embodiment, only unique concrete record contained with high Tg polystyrene segment as branch portion, with the bonding agent of butyl acrylate base polymer segment as the graft copolymer of bar portion.And, in the patent documentation 1 in the disclosed bonding agent, be necessary to carry out the chemical crosslinking processing in order to bring into play its adhesion characteristic, crosslinked in order to carry out, low Tg polymer segment (bar part) to the above-mentioned graft copolymer that constitutes the matrix that forms bonding agent imports functional groups such as hydroxyl or carboxyl in advance, when coating adhesive, in binder solution, add crosslinking chemical (" the コ ロ ネ one ト L " of 3 functional isocyanate compounds etc.) and carry out chemical crosslinking.Therefore, the bonding agent of record in the patent documentation 1 is necessary to carry out post-processing steps such as chemical crosslinking when making adhesive optical film, and the low and easy generation of productivity is because the inequality of the bond properties that crosslinked inequality caused.
In addition, the bonding agent of record in the citing document 2 and 3, since form the weight-average molecular weight of acrylic acid series polymeric compounds of matrix of bonding agent high, be more than 1,000,000, the solution viscosity height, be necessary to use a large amount of organic solvent amounts for the low viscous binder solution that obtains the coating excellence, reduce the solid component concentration of binder solution.Aspects such as the long-timeization existing problems of step are removed in the use of a large amount of organic solvents, the solvent after environmental pollution, coating.And, in the bonding agent of in citing document 2 and 3, putting down in writing, with in the citing document 1 record bonding agent similarly, in the acrylic acid series polymeric compounds that forms matrix, import in advance and be used for reacting carboxyl or other functional group that produces chemical crosslinking and show adhesion characteristic with crosslinking chemical (" the コ ロ ネ one ト L " of 3 functional isocyanate compounds etc.), when coating adhesive, in binder solution, add crosslinking chemical and carry out chemical crosslinking, so when making adhesive optical film, be necessary to carry out in addition post-processing steps such as chemical crosslinking, the low and easy generation of productivity is because the inequality of the bond properties that crosslinked inequality caused.
In addition, the known heat-fusible adhesive (with reference to patent documentation 4 and 5) that contains the acrylic acid series triblock copolymer, the technical scheme that this heat-fusible adhesive is used for blooming is not disclosed in these documents, in addition, do not make solvent-based adhesive in the organic solvent and substitute the technical scheme that this heat-fusible adhesive fusion is used for blooming and disclose this heat-fusible adhesive is dissolved in.
Patent documentation 1: Japanese kokai publication hei 7-82542 communique
Patent documentation 2: TOHKEMY 2003-329837 communique
Patent documentation 3: TOHKEMY 2004-58289 communique
Patent documentation 4: Japanese kokai publication hei 11-302617 communique
Patent documentation 5: Japanese kokai publication hei 11-323072 communique
Patent documentation 6: Japanese kokai publication hei 6-93060 communique
Patent documentation 7: the special fair 7-25859 communique of Japan
Patent documentation 8: Japanese kokai publication hei 11-335432 communique
Non-patent literature 1: " Macromol.Chem.Phys. ", 2000,201 volumes, p.1108～1114
Summary of the invention
The objective of the invention is to; be provided at and paste blooming on the adherend or when on blooming, pasting diaphragm; can residual adhesive; can peel off with suitable peel strength; re-workability (リ ワ one Network) excellence; even and be exposed to the reduction that also can not produce bounding force under heated condition or the humid tropical condition or foaming etc., and can the good adhesion characteristic of long term maintenance, the pressure-sensitive adhesive for optical films of excellent in te pins of durability.
And, the objective of the invention is to, providing does not need to carry out chemical crosslinking and handles, and does not carry out the pressure-sensitive adhesive for optical films that the adhesive optical film etc. of bond properties and endurance quality excellence just can productivity be made in chemical crosslinking well.
Further, the objective of the invention is to, provide when being dissolved in the organic solvent to prepare low viscous solution, reduce the pressure-sensitive adhesive for optical films of the solution-type of the consumption of organic solvent and coating and operability excellence thus.
In addition; the objective of the invention is to; adhesive optical film and adhesive optical film diaphragm with the adhesive phase that is formed by above-mentioned pressure-sensitive adhesive for optical films are provided, and use above-mentioned adhesive optical film and/or the adhesive optical film image display device of diaphragm.
The inventor studies intensively in order to address the above problem, found that, if using with specific acrylic acid series triblock copolymer is that glass transition temperature is that acrylic acrylate polymer blocks below-20 ℃ is as central block, it is methacrylic acid propenyl ester polymer more than 100 ℃ that its two ends are combined with glass transition temperature respectively, and weight-average molecular weight (Mw) is 50000～300000, molecular weight distribution (Mw/Mn) is 1.0～1.5, the content of the acrylic acid propenyl ester polymer block of central authorities is that the acrylic acid series three block analog copolymers of 50～95 quality % prepare pressure-sensitive adhesive for optical films, does not then carry out the chemical crosslinking processing and just obtains re-workability, adhesion characteristic, thermotolerance, the pressure-sensitive adhesive for optical films of excellents such as permanance.
In addition, the inventor finds, above-mentioned specific acrylic acid series triblock copolymer is dissolved in the solution that obtains in the organic solvent, even concentration height, solution viscosity is also low, when the consumption that operability or excellent storage stability when the bonding agent that will contain this acrylic acid series triblock copolymer is coated on the base material, the solvent during the preparation pressure-sensitive adhesive for optical films after environmental pollution or the coating are removed the organic solvent that step causes load reduces, can be coated on the base material.
Further, the inventor finds, if this moment, acid was triblock copolymer as aforesaid propylene, using weight-average molecular weight (Mw) is 50000 or more and less than 100000 acrylic acid series triblock copolymer and weight-average molecular weight (Mw) to be the acrylic acid series triblock copolymer that 100000～300000 acrylic acid series triblock copolymer forms with specific mass ratio cooperation, then can be with the bonding rerum natura (bounding force of pressure-sensitive adhesive for optical films, creep etc.), volume rerum natura (dynamic viscoelastic etc.) etc. more simply and successfully is adjusted into required rerum natura, and further improves the re-workability and the permanance of this pressure-sensitive adhesive for optical films.
In addition, the inventor finds, if when using above-mentioned specific acrylic acid series triblock copolymer with specified quantitative, with specified quantitative use specific acrylic acid series diblock copolymer, be that the weight-average molecular weight (Mw) of methacrylate polymer block and each 1 be combined into of alkyl acrylate polymer blocks is 50000～300000, molecular weight distribution (Mw/Mn) be 1.0～1.5 and the content of alkyl acrylate polymer blocks be the diblock copolymer of 50～95 quality %, then obtain the more excellent pressure-sensitive adhesive for optical films of re-workability.
Further, the inventor finds, if make the energy storage elastic modulus (storage KURA spring rate of this pressure-sensitive adhesive for optical films this moment) in specific scope, then the following that the distortion of base material or adherend, expansion, contraction etc. are changed increases, the stress that base material or adherend are applied reduces, more stable bounding force and the permanance of long-term performance finished the present invention based on above-mentioned various discoveries.
That is, the present invention is
(1) pressure-sensitive adhesive for optical films of cross-linking type non-chemically, it is characterized in that, based on the gross mass of all solids composition that contains in the bonding agent, contain with the ratio more than the 60 quality % possess following condition (E1), (E2), (E3) and acrylic acid series triblock copolymer (I) (E4)
Zero acrylic acid series triblock copolymer (I):
(E1) the acrylic acid series triblock copolymer shown in the following general formula (1),
A1-B-A2 (1)
(in the formula, A1 and A2 represent independently that respectively glass transition temperature is the methacrylate polymer block more than 100 ℃, and B represents that glass transition temperature is the alkyl acrylate polymer blocks below-20 ℃),
(E2) content of polymer blocks B is 50～95 quality %,
(E3) weight-average molecular weight (Mw) is 50000～300000, and
(E4) molecular weight distribution (Mw/Mn) is 1.0～1.5.
Further, the present invention is
(2) pressure-sensitive adhesive for optical films of above-mentioned (1), wherein, acrylic acid series triblock copolymer (I) is to possess following condition (E1), (E2), (E3 ') and acrylic acid series triblock copolymer (Ia) (E4) and possess following condition (E1), (E2), (E3 ") and acrylic acid series triblock copolymer (Ib) (E4) with acrylic acid series triblock copolymer (Ia): the mass ratio of acrylic acid series triblock copolymer (Ib)=45: 55～75: 25 cooperates and forms
Zero acrylic acid series triblock copolymer (Ia):
(E1) the acrylic acid series triblock copolymer shown in the following general formula (1),
A1-B-A2 (1)
(in the formula, A1 and A2 represent independently that respectively glass transition temperature is the methacrylate polymer block more than 100 ℃, and B represents that glass transition temperature is the alkyl acrylate polymer blocks below-20 ℃),
(E2) content of polymer blocks B is 50～95 quality %,
(E3 ') weight-average molecular weight (Mw) is more than 50000 and less than 100000, and
(E4) molecular weight distribution (Mw/Mn) is 1.0～1.5.
Zero acrylic acid series triblock copolymer (Ib):
(E1) the acrylic acid series triblock copolymer shown in the following general formula (1),
A1-B-A2 (1)
(in the formula, A1 and A2 represent independently that respectively glass transition temperature is the methacrylate polymer block more than 100 ℃, and B represents that glass transition temperature is the alkyl acrylate polymer blocks below-20 ℃),
(E2) content of polymer blocks B is 50～95 quality %,
(E3 ") weight-average molecular weight (Mw) is 100000～300000, and
(E4) molecular weight distribution (Mw/Mn) is 1.0～1.5.
And the present invention is
(3) pressure-sensitive adhesive for optical films of above-mentioned (2), wherein, the weight-average molecular weight (Mw) of acrylic acid series triblock copolymer (Ib) is 100000～200000.
(4) pressure-sensitive adhesive for optical films of above-mentioned (2) or (3), wherein, the content of polymer blocks B is 50～70 quality % in the acrylic acid series triblock copolymer (Ia), the content of polymer blocks B is 65～95 quality % in the acrylic acid series triblock copolymer (Ib).
(5) any one pressure-sensitive adhesive for optical films in above-mentioned (2)～(4), wherein, as acrylic acid series triblock copolymer (Ib), use to possess above-mentioned condition (E1), (E2) and (E4) and weight-average molecular weight (Mw) be more than 100000 and less than 120000 acrylic acid series triblock copolymer (Ib-1) and possess above-mentioned condition (E1), (E2) and (E4) and weight-average molecular weight (Mw) be 120000～200000 acrylic acid series triblock copolymer (Ib-2) with acrylic acid series triblock copolymer (Ib-1): the mass ratio of acrylic acid series triblock copolymer (Ib-2)=10: 90～90: 10 cooperates the acrylic acid series triblock copolymer that forms.And
(6) any one pressure-sensitive adhesive for optical films in above-mentioned (1)～(5), wherein, constitute acrylic acid series triblock copolymer (I), acrylic acid series triblock copolymer (Ia), acrylic acid series triblock copolymer (Ib), acrylic acid series triblock copolymer (Ib-1) or acrylic acid series triblock copolymer (Ib-2) the methacrylate polymer block between normality be more than 65%.
In addition, the present invention is
(7) any one pressure-sensitive adhesive for optical films in above-mentioned (1)～(6), wherein, gross mass based on all solids composition that contains in the bonding agent, further contain with the ratio of 3～25 quality % possess following condition (F1), (F2), (F3) and acrylic acid series diblock copolymer (II) (F4)
Zero acrylic acid series diblock copolymer (II)
(F1) the acrylic acid series diblock copolymer shown in the following general formula (2),
C-D (2)
(in the formula, C represents that methacrylate polymer block, D represent the alkyl acrylate polymer blocks),
(F2) content of polymer blocks D is 50～95 quality %,
(F3) weight-average molecular weight (Mw) is 50000～300000, and
(F4) molecular weight distribution (Mw/Mn) is 1.0～1.5.
And the present invention is
(8) any one pressure-sensitive adhesive for optical films in above-mentioned (1)～(7), wherein, when under the frequency of frequency 6.28rad/s, measuring the dynamic viscoelastic of bonding agent, the energy storage elastic modulus under 23 ℃ [G ' (23 ℃)] be 1.0 * 10 5～8.0 * 10 5Pa, and the energy storage elastic modulus under 90 ℃ [G ' (90 ℃)] be 7.0 * 10 4～6.0 * 10 5Pa.
(9) any one pressure-sensitive adhesive for optical films in above-mentioned (1)～(8) is the solvent-based adhesive that is dissolved in the organic solvent.
(10) any one pressure-sensitive adhesive for optical films in above-mentioned (1)～(9) wherein, is made the toluene solution that solid component concentration is 45 quality %, and the solution viscosity of measuring with Brookfield viscometer under 25 ℃ temperature is 1000～4000mPas.
(11) adhesive optical film or adhesive optical film diaphragm, it has the bonding coat that is formed by any one pressure-sensitive adhesive for optical films in above-mentioned (1)～(10), forms without the cross-linking step manufacturing.
(12) image display device wherein uses the adhesive optical film and/or the adhesive optical film diaphragm of above-mentioned (11).
With the acrylic acid series triblock copolymer (I) that possesses above-mentioned condition (E1)～(E4) pressure-sensitive adhesive for optical films of the present invention as main body; because not needing chemical crosslinking handles; do not show high cohesion even do not carry out the chemical crosslinking processing yet; have excellent re-workability, adhesion characteristic, thermotolerance, permanance etc.; so can omit cross-linking step, and can make adhesive optical film and adhesive optical film diaphragm with good processability, good productivity.
Pressure-sensitive adhesive for optical films of the present invention is owing to be cross-linking type non-chemically, in the pressure-sensitive adhesive for optical films of in the past chemical crosslinking type, become the excellent storage stability of the binder solution of problem, further, can not cause the bond properties of goods to produce unequal bad problem, have even and high performance adhesion characteristic owing to the condition in drying steps or the preservation process (temperature, air quantity, linear velocity, storage life etc.) produces crosslinked inequality.
With the of the present invention pressure-sensitive adhesive for optical films of above-mentioned specific acrylic acid series triblock copolymer (I) as main body, because when in being dissolved in organic solvent, making the bonding agent of solution-type, even the concentration height also shows low solution viscosity, so can reduce the consumption of organic solvent, and can make solid component concentration than high in the past solvent-based adhesive (solid component concentration is the above solvent-based adhesives of 35 quality %), excellent in workability such as operability the when solvent-based adhesive that this solid component concentration is high is coated with or linear velocity raising.
And, by reducing the consumption of organic solvent, reduce owing to operating environment variation or problem of environmental pollution that organic solvent caused, and the solvent that can reduce after the coating is removed needed time of step or heat energy etc.
Further, by making the high solvent-based adhesive of solid component concentration, can realize transportation cost reduction, can realize that by reducing the reinforced number of times of bonding agent groove productivity improves.
Particularly among the present invention, possesses above-mentioned condition (E1) with the extra fine quality of stipulating among the present invention than using, (E2) and weight-average molecular weight (E4) (Mw) be more than 50000 and less than 100000 acrylic acid series triblock copolymer (Ia), with possess above-mentioned condition (E1), (E2) and weight-average molecular weight (E4) (Mw) be 100000～300000 acrylic acid series triblock copolymer (Ib) pressure-sensitive adhesive for optical films as acrylic acid series triblock copolymer (I), can be with bonding rerum natura (bounding force, creep etc.), volume rerum natura (dynamic viscoelastic etc.) etc. more simply and successfully is adjusted into required rerum natura, and permanance is more excellent, bounding force through the time change still less, still keep excellent re-workability after the long-time heating.
In the pressure-sensitive adhesive for optical films of the present invention, when cooperating acrylic acid series triblock copolymer (I), gross mass based on all solids composition that contains in the bonding agent, the pressure-sensitive adhesive for optical films that cooperates the specific acrylic acid series diblock copolymer (II) that possesses above-mentioned condition (F1)～(F4) to obtain with the ratio of 3～25 quality %, bonding agent is good for the wetting state of adherend, bounding force through the time change little, the re-workability excellence.
In addition, in the pressure-sensitive adhesive for optical films of the present invention, during with the frequency measurement dynamic viscoelastic of 6.28rad/s, the energy storage elastic modulus under 23 ℃ [G ' (23 ℃)] be 1.0 * 10 5～8.0 * 10 5Energy storage elastic modulus under Pa and 90 ℃ [G ' (90 ℃)] be 7.0 * 10 4～6.0 * 10 5The pressure-sensitive adhesive for optical films of Pa, good to the following that the distortion of base material or adherend, expansion, contraction etc. change, the stress that base material or adherend are applied reduces more stable bounding force and the permanance of long-term performance.
Embodiment
Below the present invention is carried out specific description.
The present invention relates to pressure-sensitive adhesive for optical films.
" pressure-sensitive adhesive for optical films " of the present invention; be that the various films that use in optical applications (are not limited; polarizing coating for example; polarization plates; phase retardation film; film is amplified at the visual angle; brightness improves film; antireflection film; antiglare film; color filter; light guide plate; diffusion barrier; prismatic lens; electromagnetic shielding film; near-infrared absorption film; be compounded with the functional complex optical film of multiple optical function etc.) part or all of one or both sides form employed bonding agent on the adherend that adhesive phase pastes blooming other, and the general name that diaphragm is pasted employed bonding agent on the surface of blooming for the surface of protecting above-mentioned blooming.
The acrylic acid series triblock copolymer (I) that uses in the pressure-sensitive adhesive for optical films of the present invention is the acrylic acid series triblock copolymer that possesses following condition (E1)～(E2),
(E1) the acrylic acid series triblock copolymer shown in the following general formula (1),
A1-B-A2(1)
(in the formula, A1 and A2 represent independently that respectively glass transition temperature is the methacrylate polymer block more than 100 ℃, and B represents that glass transition temperature is the alkyl acrylate polymer blocks below-20 ℃),
(E2) weight-average molecular weight (Mw) is 50000～300000,
(E3) molecular weight distribution (Mw/Mn) is 1.0～1.5, and
(E4) content of polymer blocks B is 50～95 quality %.
As the acrylic acid series triblock copolymer (I) of the main body of pressure-sensitive adhesive for optical films of the present invention is that bonding contains the formula that the polymer blocks B of alkyl acrylate forms between 2 polymer blocks A1 that contain methacrylate polymer and A2: the acrylic acid series triblock copolymer shown in the A1-B-A2 [above-mentioned condition (E1)].
2 polymer blocks A1 and A2 in the acrylic acid series triblock copolymer (I) contain the polymer blocks that glass transition temperature is the methacrylate polymer more than 100 ℃.The polymer blocks A1 and the A2 performance that contain glass transition temperature and be the methacrylate polymer more than 100 ℃ (are restrained phase) (pseudo-crosslinking points (Be physically is like frame Bridge point) mutually as the constraint in the acrylic acid series triblock copolymer (I) that forms micro phase separation structure under the common serviceability temperature of bonding agent) effect.Therefore, pressure-sensitive adhesive for optical films of the present invention, show the pressure-sensitive adhesive for optical films of putting down in writing in the above-mentioned patent documentation 1～3 of bounding force in the past with carrying out chemical crosslinking different, there is no need to cooperate crosslinking chemical, even do not carry out chemical crosslinking, also show sufficient cohesiveness, adhesion characteristic and permanance that performance is excellent.
From permanance, thermotolerance, the following of base material distortion, suitable stress retentivity aspect are considered, polymer blocks A1 in the preferred acrylic acid series triblock copolymer (I) and A2 are that glass transition temperature is 100～120 ℃, 100～150 ℃ methacrylate polymer block particularly.
In the acrylic acid series triblock copolymer (I), need only 2 polymer blocks A1 and A2 and contain the polymer blocks that glass transition temperature is the methacrylate polymer more than 100 ℃, then can contain identical polymkeric substance [molecular weight, monomer composition, spatial structure (normality etc.) etc. are identical identical methacrylate polymer mutually] or different polymkeric substance [the mutual different methacrylate polymer more than a kind or 2 kinds in molecular weight, monomer composition, the spatial structure (normality etc.) etc.].
As the alkyl methacrylate unit that constitutes polymer blocks A1 and A2, for example can enumerate, contain methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, n-BMA, the metering system tert-butyl acrylate, the just own ester of methacrylic acid, the methacrylic acid cyclohexyl ester, methacrylic acid 2-Octyl Nitrite, n octyl methacrylate, lauryl methacrylate, methacrylic acid tridecyl ester, the methacrylic acid stearyl ester, the unit of alkyl methacrylates such as isobornyl methacrylate, polymer blocks A1 and A2 can only form by a kind in the above-mentioned alkyl methacrylate unit or by forming more than 2 kinds.
Wherein, can easily obtain with economic price from the raw material methyl methacrylate, and polymethylmethacrylate has excellent permanance and the weatherability aspect is considered, preferred polymers block A1 and A2 contain polymethylmethacrylate.
Constitute the polymer blocks B of acrylic acid series triblock copolymer (I) and be the polymer blocks below-20 ℃, then the kind of the acrylic acid alkyl ester units that constitutes polymer blocks B or one-tenth are not grouped into and limit especially so long as contain the glass transition temperature of alkyl acrylate.
Glass transition temperature makes pressure-sensitive adhesive for optical films of the present invention (following " bonding agent of the present invention " or " bonding agent " of only being called sometimes) show suitable bounding force and good re-workability for the polymer blocks B below-20 ℃ gives excellent flexibility and wetting state to the acrylic acid series triblock copolymer (I) that forms micro phase separation structure under common serviceability temperature.
Wherein, the excellent in te pins of durability aspect under the cryogenic conditions considers that the preferred polymers B block contains glass transition temperature for below-30 ℃, particularly-40 ℃～and-80 ℃ acrylic acid alkyl ester polymer.
As the acrylic acid alkyl ester units that constitutes polymer blocks B, for example can enumerate, the unit that contains alkyl acrylates such as the just own ester of methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, tert-butyl acrylate, acrylic acid, cyclohexyl acrylate, 2-EHA, acrylic acid n-octyl, dodecylacrylate, tridecyl acrylate, stearyl acrylate ester, polymer blocks B can be formed by a kind in the aforesaid propylene acid alkyl ester unit or by forming more than 2 kinds.
Wherein, from the glass transition temperature of polymer blocks B be below-20 ℃, bonding agent bounding force and viscosity at low temperatures is good, and the bounding force in the time of can suppressing to peel off at a high speed raises and tears phenomenon (ジ Star ピ ン グ Now resembles) aspect and consider that the preferred polymers B block is by constituting more than a kind or 2 kinds in the unit that contains propyl acrylate, n-butyl acrylate, 2-EHA, acrylic acid n-octyl.
Can be used as from n-butyl acrylate and the own ester of acrylic acid 2-hexyl and generally to obtain with cheapness with chemicals, and polymer blocks A and polymer blocks B are separated obviously, the pseudo-crosslinking points of polymer A can be not destroyed, cohesiveness height and excellent in te pins of durability aspect as bonding agent consider that special preferred polymers B block is made of n-butyl acrylate unit and/or 2-EHA unit.
Constitute polymer blocks A1 and the A2 and the polymer blocks B of acrylic acid series triblock copolymer (I), in the scope of not damaging effect of the present invention, if a small amount of (common quality with respect to each polymer blocks is the ratio below the 10 quality %) then can have other monomeric unit.The monomeric unit of other that can have as polymer blocks A1 and A2 and polymer blocks B, can for example enumerate and contain (methyl) acrylic acid methoxyl ethyl ester and (refer to acrylic acid methoxyl ethyl ester or methacrylic acid methoxy base ethyl ester, below identical), (methyl) acrylic acid ethoxy ethyl ester, (methyl) acrylic acid diethylamino ethyl ester, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-amino ethyl ester, (methyl) acrylic acid glycidyl esters, (methyl) acrylic acid tetrahydro furfuryl ester etc. has (methyl) acrylate of functional group, (methyl) acrylic acid, crotonic acid, maleic acid, maleic anhydride, fumaric acid, (methyl) acrylamide etc. has the vinyl monomer of carboxyl, styrene, α-Jia Jibenyixi, aromatic ethylene base class monomers such as p-methylstyrene, butadiene, isoprene equiconjugate dienes monomer, ethene, olefin monomers such as propylene, 6-caprolactone, the unit of lactone monomers such as valerolactone etc., can contain as required in these monomeric units more than a kind or 2 kinds.
The ratio of polymer blocks B based on the quality of acrylic acid series triblock copolymer (I), is the above-mentioned conditions of 50～95 quality %[(E2) in the acrylic acid series triblock copolymer (I)], be preferably 60～85 quality %, more preferably 65～80 quality %.
Content by making polymer blocks B in the acrylic acid series triblock copolymer (I) makes the bounding force of bonding agent stable in above-mentioned scope.
If the content of polymer blocks B is less than the then bounding force reduction of bonding agent of 50 quality % in the acrylic acid series triblock copolymer (I), on the other hand if surpass 95 quality % then owing to form the polymer blocks A1 of pseudo-crosslinking points and the relative reduction of content of A2 causes cohesiveness to reduce, the permanance reduction of bonding agent.
The weight-average molecular weight (Mw) of acrylic acid series triblock copolymer (I) is the above-mentioned condition of 50000～300000[(E3)], consider from permanance and re-workability aspect, be preferably 60000～250000, more preferably 70000～200000.
If the weight-average molecular weight (Mw) of acrylic acid series triblock copolymer (I) is less than 50000, then the cohesiveness of bonding agent is insufficient, uses bonding agent to paste blooming on the adherend or when pasting diaphragm on the blooming, easily peels off poor durability.On the other hand; if the weight-average molecular weight (Mw) of acrylic acid series triblock copolymer (I) is greater than 300000; then the medium bounding force of preservation process at goods slowly raises, in order to eliminate entering or position deviation and peel off blooming or diaphragm and reprocessing when fitting the once more difficulty that becomes of fold, bubble, foreign matter.In addition, if the weight-average molecular weight (Mw) of acrylic acid series triblock copolymer (I) is greater than 300000, then solution viscosity increases, and can not be coated with high concentration, and solvent load increases.
The molecular weight distribution (Mw/Mn) of acrylic acid series triblock copolymer (I) is the above-mentioned condition of 1.0～1.5[(E4)], increase from bonding agent cohesiveness at high temperature, the more excellent aspect of permanance considers that molecular weight distribution (Mw/Mn) is preferably 1.0～1.4, more preferably 1.0～1.3.
If the molecular weight distribution (Mw/Mn) of acrylic acid series triblock copolymer (I) then can not be ignored the influence of low molecular weight compositions greater than 1.5, the bad problems such as adhesive residue when easily producing cohesiveness reduction or reprocessing.
Wherein, the weight-average molecular weight (Mw) of the acrylic acid series diblock copolymer of the acrylic acid series triblock copolymer in this instructions, following record, number-average molecular weight (Mn) and molecular weight distribution (Mw/Mn) are the values of trying to achieve with the method for putting down in writing among the following embodiment.
Can contain the a kind of acrylic acid series triblock copolymer that satisfies above-mentioned condition (E1)～(E4) or satisfy the acrylic acid series triblock copolymer more than 2 kinds or 3 kinds of above-mentioned condition (E1)～(E4) as the acrylic acid series triblock copolymer (I) of the main body of pressure-sensitive adhesive for optical films of the present invention.
Particularly in bonding agent of the present invention, acrylic acid series triblock copolymer (I) as main body, possesses following condition (E1) if use, (E2), (E3 ') and acrylic acid series triblock copolymer (Ia) (E4) and possess following condition (E1), (E2), (E3 ") and acrylic acid series triblock copolymer (Ib) (E4) are with acrylic acid series triblock copolymer (Ia): the mass ratio of acrylic acid series triblock copolymer (Ib)=45: 55～75: 25; preferred 50: 50～70: 30 mass ratio; more preferably 60: 40～70: 30 mass ratio cooperates the acrylic acid series triblock copolymer (I) that forms; then can be with the bonding rerum natura (bounding force; creep etc.) of bonding agent; volume rerum natura (バ Le Network rerum natura) (dynamic viscoelastic etc.) etc. more simply and successfully is adjusted into required rerum natura, and the permanance of bonding agent, re-workability further improves.
Zero acrylic acid series triblock copolymer (Ia):
(E1) the acrylic acid series triblock copolymer shown in the following general formula (1),
A1-B-A2 (1)
(in the formula, A1 and A2 represent independently that respectively glass transition temperature is the methacrylate polymer block more than 100 ℃, and B represents that glass transition temperature is the alkyl acrylate polymer blocks below-20 ℃),
(E2) content of polymer blocks B is 50～95 quality %,
(E3 ') weight-average molecular weight (Mw) is more than 50000 and less than 100000, and
(E4) molecular weight distribution (Mw/Mn) is 1.0～1.5.
Zero acrylic acid series triblock copolymer (Ib):
(E1) the acrylic acid series triblock copolymer shown in the following general formula (1),
A1-B-A2(1)
(in the formula, A1 and A2 represent independently that respectively glass transition temperature is the methacrylate polymer block more than 100 ℃, and B represents that glass transition temperature is the alkyl acrylate polymer blocks below-20 ℃),
(E2) content of polymer blocks B is 50～95 quality %,
(E3 ") weight-average molecular weight (Mw) is 100000～300000, and
(E4) molecular weight distribution (Mw/Mn) is 1.0～1.5.
As acrylic acid series triblock copolymer (I), use aforesaid propylene acid be triblock copolymer (Ia) and acrylic acid series triblock copolymer (Ib) cooperation form the acrylic acid series triblock copolymer time, as acrylic acid series triblock copolymer (Ia), the preferred use possesses above-mentioned condition (E1), (E2) and (E4) and weight-average molecular weight (Mw) be 50000～90000, and then be 55000～85000,60000～75000 acrylic acid series triblock copolymer particularly, in addition, as acrylic acid series triblock copolymer (Ib), the preferred use possesses above-mentioned condition (E1), (E2) and (E4) and weight-average molecular weight (Mw) be 100000～200000, and then be 105000～190000,110000～180000 acrylic acid series triblock copolymer particularly.Thus, the permanance of bonding agent, re-workability, to because the following of the expansion of the blooming that influence caused of temperature or humidity, contraction is better.
In addition, as acrylic acid series triblock copolymer (I), when using acrylic acid series triblock copolymer (Ia) and acrylic acid series triblock copolymer (Ib) to cooperate the acrylic acid series triblock copolymer that forms, if with the content of polymer blocks B is that the content of the acrylic acid series triblock copolymer (Ia) of 50～70 quality % and polymer blocks B is that the acrylic acid series triblock copolymer (Ib) of 65～95 quality % is used, then the molecular weight of the polymer blocks A1 of the molecular weight of the polymer blocks A1 of acrylic acid series triblock copolymer (Ia) and A2 and acrylic acid series triblock copolymer (Ib) and A2 is approaching, compatibility between the polymer blocks of the physical crosslinking effect of performance acrylic acid series triblock copolymer (Ia) and acrylic acid series triblock copolymer (Ib) improves, by the physical crosslinking formation reticulate texture of acrylic acid series triblock copolymer (Ia) with acrylic acid series triblock copolymer (Ib), the permanance of bonding agent further improves.
In addition, as acrylic acid series triblock copolymer (I), with acrylic acid series triblock copolymer (Ia) and acrylic acid series triblock copolymer (Ib) when being used, as acrylic acid series triblock copolymer (Ib), possesses above-mentioned condition (E1) if use, (E2) and (E4) and weight-average molecular weight (Mw) be more than 100000 and less than 120000 acrylic acid series triblock copolymer (Ib-1) and possess above-mentioned condition (E1), (E2) and (E4) and weight-average molecular weight (Mw) be 120000～200000 acrylic acid series triblock copolymer (Ib-2) with acrylic acid series triblock copolymer (Ib-1): acrylic acid series triblock copolymer (Ib-2)=10: 90～90: 10, preferred 50: 50～90: 10, the acrylic acid series triblock copolymer that more preferably 60: 40～80: 20 mass ratio mixes, then can be with the bonding rerum natura (bounding force of pressure-sensitive adhesive for optical films, creep etc.), volume rerum natura (dynamic viscoelastic etc.) etc. more simply and successfully is adjusted into required rerum natura, and permanance and re-workability excellence, can be coated with high concentration, can reduce consumption of organic solvent.
In acrylic acid series triblock copolymer (I), acrylic acid series triblock copolymer (Ia), acrylic acid series triblock copolymer (Ib), acrylic acid series triblock copolymer (Ib-1) or the acrylic acid series triblock copolymer (Ib-2), constitute these triblock copolymers the methacrylate polymer block between normality be preferably more than 65% more preferably 70～95%.By make this polymer blocks between normality be 65%, the permanance of bonding agent (continuation of adhesion characteristic) is good.
In the bonding agent of the present invention, gross mass with respect to the solid constituent that contains in the bonding agent, aforesaid propylene acid is that the content of triblock copolymer (I) is necessary for more than the 60 quality %, be preferably more than the 75 quality %, 80 quality % above [acrylic acid series triblock copolymer (Ia) and acrylic acid series triblock copolymer (Ib) are being cooperated when being used as acrylic acid series triblock copolymer (I), above-mentioned content is both total amounts] more preferably.
With respect to the gross mass of the solid constituent that contains in the bonding agent, if the content of acrylic acid series triblock copolymer (I) is less than 60 quality %, then cohesiveness reduces, and the permanance of bonding agent (continuation of bounding force) reduces.
Bonding agent of the present invention when containing aforesaid propylene acid and being triblock copolymer (I), can contain as required possess following condition (F1), (F2), (F3) and acrylic acid series diblock copolymer (II) (F4).
Zero acrylic acid series diblock copolymer (II)
(F1) the acrylic acid series diblock copolymer shown in the following general formula (2),
C-D (2)
(in the formula, C represents that methacrylate polymer block, D represent the alkyl acrylate polymer blocks),
(F2) content of polymer blocks D is 50～95 quality %,
(F3) weight-average molecular weight (Mw) is 50000～300000, and
(F4) molecular weight distribution (Mw/Mn) is 1.0～1.5.
Bonding agent of the present invention is when containing aforesaid propylene acid and being triblock copolymer (I), when further containing acrylic acid series diblock copolymer (II), the content of acrylic acid series diblock copolymer (II), gross mass with respect to all solids composition of content in the bonding agent, be preferably 3～25 quality %, more preferably 3～20 quality %.
If contain acrylic acid series diblock copolymer (II) with above-mentioned amount, then bonding agent improves for the wetting state of adherend, bounding force through the time change and reduce, can obtain the pressure-sensitive adhesive for optical films of re-workability excellence.If the content of acrylic acid series diblock copolymer (II) surpasses 25 quality %, then the cohesiveness of bonding agent reduces, and permanance (long term maintenance tacky state) might variation.
In the acrylic acid series diblock copolymer (II), polymer blocks C is preferably and contains the polymer blocks that glass transition temperature is the methacrylate polymer more than 50 ℃, in addition, polymer blocks D is preferably and contains the polymer blocks of glass transition temperature for the acrylic acid alkyl ester polymer below-20 ℃.
Further, the polymer blocks C of acrylic acid series diblock copolymer (II) preferably with bonding agent in the polymer blocks A of principal ingredient acrylic acid series triblock copolymer (I) compatible, in addition, preferably the polymer blocks B with acrylic acid series triblock copolymer (I) is compatible for the polymer blocks D of acrylic acid series diblock copolymer (II).
Thus, the polymer blocks C of acrylic acid series diblock copolymer (II) is contained polymer blocks A1 in the acrylic acid series triblock copolymer (I) and the constraint of A2 retrains mutually, has prevented the reduction of cohesiveness.In addition, the unconfinement that the polymer blocks D of acrylic acid series diblock copolymer (II) is present in the polymer blocks B that contains acrylic acid series triblock copolymer (I) mutually in, with the adhesion process at the interface of adherend in, wetting state improves, and shows stable bounding force from the initial stage of fitting.
In the acrylic acid series diblock copolymer (II), as the alkyl methacrylate unit that constitutes polymer blocks C, for example can enumerate, contain methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, n-BMA, the metering system tert-butyl acrylate, the just own ester of methacrylic acid, cyclohexyl methacrylate, methacrylic acid 2-Octyl Nitrite, n octyl methacrylate, lauryl methacrylate, methacrylic acid tridecyl ester, the methacrylic acid stearyl ester, the unit of alkyl methacrylates such as isobornyl methacrylate, polymer blocks C can only form by a kind in the above-mentioned alkyl methacrylate unit, or by forming more than 2 kinds.Wherein, can easily obtain with economic price from the raw material methyl methacrylate, and polymethylmethacrylate has excellent permanance and the weatherability aspect is considered, preferred polymers block C contains polymethylmethacrylate.
In the acrylic acid series diblock copolymer (II), as the acrylic acid alkyl ester units that constitutes polymer blocks D, for example can enumerate, the unit that contains alkyl acrylates such as the just own ester of methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, tert-butyl acrylate, acrylic acid, cyclohexyl acrylate, 2-EHA, acrylic acid n-octyl, dodecylacrylate, tridecyl acrylate, stearyl acrylate ester, polymer blocks D can only form by a kind in the aforesaid propylene acid alkyl ester unit, or by forming more than 2 kinds.
Wherein, polymer blocks D is preferably by constituting more than a kind or 2 kinds in the unit that contains propyl acrylate, n-butyl acrylate, 2-EHA, acrylic acid n-octyl, thus, the glass transition temperature of polymer blocks D is below-20 ℃, bonding agent bounding force and viscosity at low temperatures is good, and the bounding force can suppress to peel off at a high speed the time raises and tears phenomenon.In the above-mentioned monomer, n-butyl acrylate and 2-EHA can be used as and generally obtain with cheapness with chemicals.
Constitute the polymer blocks C and the polymer blocks D of acrylic acid series diblock copolymer (II), in the scope of not damaging effect of the present invention, if a small amount of (common quality with respect to each polymer blocks is the ratio below the 10 quality %) then can have other monomeric unit.The monomeric unit of other that can have as polymer blocks C and polymer blocks D, can for example enumerate and contain (methyl) acrylic acid methoxyl ethyl ester, (methyl) acrylic acid ethoxy ethyl ester, (methyl) acrylic acid diethylamino ethyl ester, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-amino ethyl ester, (methyl) acrylic acid glycidyl esters, (methyl) acrylic acid tetrahydro furfuryl ester etc. has (methyl) acrylate of functional group, (methyl) acrylic acid, crotonic acid, maleic acid, maleic anhydride, fumaric acid, (methyl) acrylamide etc. has the vinyl monomer of carboxyl, styrene, α-Jia Jibenyixi, aromatic ethylene base class monomers such as p-methylstyrene, butadiene, isoprene equiconjugate dienes monomer, ethene, olefin monomers such as propylene, 6-caprolactone, the unit of lactone monomers such as valerolactone etc., can have as required in these monomeric units more than a kind or 2 kinds.
The ratio of polymer blocks D with respect to the quality of acrylic acid series diblock copolymer (II), is the above-mentioned conditions of 50～95 quality %[(F2) in the acrylic acid series diblock copolymer (II)], be preferably 70～95 quality %.
Content by making polymer blocks B in the acrylic acid series triblock copolymer (I) makes the bounding force of bonding agent stable in above-mentioned scope.
If the content of polymer blocks B is less than the then bounding force reduction of bonding agent of 50 quality % in the acrylic acid series triblock copolymer (I), if surpass 95 quality % then owing to relative reduction of content of the polymer blocks C that forms pseudo-crosslinking points causes cohesiveness to reduce, the permanance of bonding agent might variation on the other hand.
The weight-average molecular weight (Mw) of acrylic acid diblock copolymer (II) is the above-mentioned condition of 50000～300000[(F3)], consider from permanance and re-workability aspect, be preferably 60000～250000, more preferably 70000～200000.
If the weight-average molecular weight (Mw) of acrylic acid series diblock copolymer (II) is less than 50000; then the cohesiveness of bonding agent is insufficient; the bonding agent that use contains acrylic acid series triblock copolymer (I) and acrylic acid series diblock copolymer (II) pastes blooming on the adherend or when pasting diaphragm on the blooming; easily peel off poor durability.On the other hand; if the weight-average molecular weight (Mw) of acrylic acid series diblock copolymer (II) is greater than 300000; then wetting state reduces; the medium bounding force of preservation process at goods slowly raises, in order to eliminate entering or position deviation and peel off blooming or diaphragm and reprocessing when fitting the once more difficulty that becomes of fold, bubble, foreign matter.
The molecular weight distribution (Mw/Mn) of acrylic acid series diblock copolymer (II) is the above-mentioned condition of 1.0～1.5[(F4)], from the cohesiveness excellence, the aspect that adherend contaminative (residual adhesive, low molecular weight compositions adhere to etc.) is low is considered, is preferably 1.0～1.4, more preferably 1.0～1.3.
The acrylic acid series triblock copolymer (I) that uses in the bonding agent of the present invention and the preparation method of acrylic acid series diblock copolymer (II), then do not limit especially as long as be met the acrylic acid series triblock copolymer or the acrylic acid series diblock copolymer of above-mentioned condition, can adopt method based on known method.Usually, as the method for the segmented copolymer that obtains narrow molecular weight distribution, employing will be as the method for the monomer reactivity polymerization of structural unit.Method as this living polymerization, for example can enumerate, organic RE metalloid complex compound be carried out the method (with reference to patent documentation 6) of polymerization as polymerization initiator, organic alkali metal compound is carried out anionic polymerisation as polymerization initiator in the presence of the inorganic acid salts such as salt of alkaline metal or earth alkali metal method (with reference to patent documentation 7), organic alkali metal compound is carried out the method (with reference to patent documentation 8) of anionic polymerisation in the presence of organo-aluminum compound as polymerization initiator, atom transfer radical polymerization method (ATRP) (with reference to non-patent literature 1) etc.
Among the above-mentioned preparation method, under the situation about being prepared by the method for in the presence of organo-aluminum compound, carrying out anionic polymerisation, because the inactivation in the polymerization midway is few, lack as the sneaking into of homopolymer of inactivation composition, the result is that the transparency of resulting bonding agent is high.In addition, because the polymerisation conversion height of monomer, the residual monomer in the goods is few, when using as pressure-sensitive adhesive for optical films, and the generation of the bubble after can suppressing to fit.Further, the molecular structure of methacrylate polymers block forms normality between height, when being used for pressure-sensitive adhesive for optical films, has the effect that improves permanance.And,, have when industrial production the few advantage of carrying capacity of environment (mainly being the electric power that the refrigerating machine that is used to control polymerization temperature is applied) owing to can under comparatively gentle temperature conditions, carry out living polymerization.Consider that from above aspect acrylic acid series triblock copolymer (I) that uses among the present invention and acrylic acid series diblock copolymer (II) preferably prepare by the method for carrying out anionic polymerisation in the presence of organo-aluminum compound.
In the presence of organo-aluminum compound, carry out anionic polymerisation process as above-mentioned, for example can adopt following method etc.: at organo-lithium compound and following general formula (III):
AlR 1R 2R 3 (III)
(in the formula, R 1, R 2And R 3Expression can have substituent alkyl, can have substituent naphthenic base, can have substituent aryl, can have substituent aralkyl, can have substituent alkoxy, can have substituent aryloxy group or N independently respectively, N-disubstituted amido, or R 1Be above-mentioned any one group, R 2And R 3Form together and can have substituent arlydene dioxy base.)
Under the existence of shown organo-aluminum compound, as required, in reaction system, further add ether compounds such as dimethyl ether, dimethoxy-ethane, diethoxyethane, 12-crown ether-4, triethylamine, N, N, N ', N '-tetramethylethylened, N, N, N '; N ", N "-five methyl diethylentriamine, 1,1; 4,7,10; 10-hexamethyl trien, pyridine, 2, nitrogen-containing compounds such as 2 '-dipyridine make (methyl) acrylic ester polymerization.
As above-mentioned organo-lithium compound, for example can enumerate, lithium methide, ethyl-lithium, the n-pro-pyl lithium, the isopropyl lithium, n-BuLi, s-butyl lithium, the isobutyl lithium, tert-butyl lithium, the n-pentyl lithium, hexyllithium, tetramethylene two lithiums, pentamethylene two lithiums, lithium alkyl and alkyl two lithiums such as hexa-methylene two lithiums, phenyl lithium, between the tolyl lithium, the p-methylphenyl lithium, the xylyl lithium, aryl lithium and aryl two lithiums such as lithium naphthalene, the benzyl lithium, the diphenyl methyl lithium, the trityl lithium, 1,1-diphenyl-3-methyl amyl lithium, α-Jia Jibenyixi base lithium, aralkyl lithium and aralkyl two lithiums such as two lithiums that reaction by di isopropenylbenzene and butyl lithium generates, the dimethylamino lithium, the diethylamino lithium, lithium amides such as lithium diisopropylamine, the methoxyl lithium, the ethoxy lithium, the positive propoxy lithium, lithium isopropoxide, the n-butoxy lithium, the sec-butoxy lithium, the tert-butoxy lithium, the amoxy lithium, own oxygen base lithium, heptan oxygen base lithium, the octyloxy lithium, the phenoxy group lithium, 4-methylphenoxy lithium, the benzyloxy lithium, lithium alkoxide such as 4-methyl benzyloxy lithium.They can use separately or also use more than 2 kinds.
In addition, as the organo-aluminum compound shown in the above-mentioned general formula (III), can enumerate trimethyl aluminium, aluminium triethyl, three n-butylaluminum, three sec-butyl aluminium, tri-tert aluminium, triisobutyl aluminium, tri-n-hexyl aluminum, tri-n-octylaluminium, three 2-ethylhexyl aluminium, trialkylaluminiums such as triphenyl aluminum, dimethyl (2,6-di-t-butyl-4-methylphenoxy) aluminium, dimethyl (2,6-di-t-butyl phenoxy group) aluminium, diethyl (2,6-di-t-butyl-4-methylphenoxy) aluminium, diethyl (2,6-di-t-butyl phenoxy group) aluminium, diisobutyl (2,6-di-t-butyl-4-methylphenoxy) aluminium, diisobutyl (2,6-di-t-butyl phenoxy group) aluminium, di-n-octyl (2,6-di-t-butyl-4-methylphenoxy) aluminium, di-n-octyl (2,6-di-t-butyl phenoxy group) dialkyl group phenoxy group aluminium such as aluminium, methyl two (2,6-di-t-butyl-4-methylphenoxy) aluminium, methyl two (2,6-di-t-butyl phenoxy group) aluminium, ethyl [2,2 '-methylene two (4-methyl-6-tert butyl phenoxy)] aluminium, ethyl two (2,6-di-t-butyl-4-methylphenoxy) aluminium, ethyl two (2,6-di-t-butyl phenoxy group) aluminium, ethyl [2,2 '-methylene two (4-methyl-6-tert butyl phenoxy)] aluminium, isobutyl two (2,6-di-t-butyl-4-methylphenoxy) aluminium, isobutyl two (2,6-di-t-butyl phenoxy group) aluminium, isobutyl [2,2 '-methylene two (4-methyl-6-tert butyl phenoxy)] aluminium, n-octyl two (2,6-di-t-butyl-4-methylphenoxy) aluminium, n-octyl two (2,6-di-t-butyl phenoxy group) aluminium, n-octyl [2,2 '-methylene two (4-methyl-6-tert butyl phenoxy)] alkyl diphenyl oxygen base aluminium such as aluminium, methoxyl two (2,6-di-t-butyl-4-methylphenoxy) aluminium, methoxyl two (2,6-di-t-butyl phenoxy group) aluminium, methoxyl [2,2 '-methylene two (4-methyl-6-tert butyl phenoxy)] aluminium, ethoxy two (2,6-di-t-butyl-4-methylphenoxy) aluminium, ethoxy two (2,6-di-t-butyl phenoxy group) aluminium, ethoxy [2,2 '-methylene two (4-methyl-6-tert butyl phenoxy)] aluminium, isopropoxy two (2,6-di-t-butyl-4-methylphenoxy) aluminium, isopropoxy two (2,6-di-t-butyl phenoxy group) aluminium, isopropoxy [2,2 '-methylene two (4-methyl-6-tert butyl phenoxy)] aluminium, tert-butoxy two (2,6-di-t-butyl-4-methylphenoxy) aluminium, tert-butoxy two (2,6-di-t-butyl phenoxy group) aluminium, tert-butoxy [2,2 '-methylene two (4-methyl-6-tert butyl phenoxy)] alkoxy two phenoxy group aluminium such as aluminium, three (2,6-di-t-butyl-4-methylphenoxy) aluminium, triple phenoxyl aluminium such as three (2,6-diphenyl phenoxy group) aluminium etc.In these organo-aluminum compounds, isobutyl two (2,6-di-t-butyl-4-methylphenoxy) aluminium, isobutyl two (2,6-di-t-butyl phenoxy group) aluminium, from processing ease, and can inactivation under comparatively gentle temperature conditions and can carry out considering aspect the polymerization of acrylate, preferred isobutyl [2,2 '-methylene two (4-methyl-6-tert butyl phenoxy)] aluminium etc.They can use separately or also use more than 2 kinds.
Bonding agent of the present invention, as solid constituent (composition beyond the organic solvent), can only contain acrylic acid series triblock copolymer (I) and do not contain other composition, also can only contain acrylic acid series triblock copolymer (I) and acrylic acid series diblock copolymer (II), can also further contain as required in tackifying resin, plastifier, other the adjuvant more than a kind or 2 kinds.
In the bonding agent of the present invention, because the gross mass of all solids composition that contains in the relative bonding agent, the content of acrylic acid series triblock copolymer (I) is more than the 60 quality %, bonding agent of the present invention contains acrylic acid series diblock copolymer (II), tackifying resin, plastifier, when other one-tenth grades in addition solid constituent of acrylic acid series triblock copolymer (I), the total content of these other solid constituent, gross mass with respect to all solids composition that contains in the bonding agent, be necessary for below the 40 quality %, be preferably below the 25 quality %, more preferably below the 20 quality %.
If in bonding agent of the present invention, cooperate tackifying resin, then regulate viscosity, bounding force and confining force easily.As tackifying resin, can use in the bonding agent in the tackifying resin that uses so far any one, for example can enumerate, natural resins such as rosin series resin, terpenic series resin, petroleum resin, benzodihydropyran-indenes are synthetic resin such as resin, phenol resin, xylene resin, phenylethylene resin series etc., can only use in them a kind or and with more than 2 kinds.
In the above-mentioned tackifying resin, from with the compatibility height of acrylic acid series triblock copolymer (I), show stable bounding force aspect and consider, the preferred terpenic series resins such as hydrogenated terpene resin, terpenes phenol that use, rosin series resins such as hydrogenated wood rosin glycerol ester, disproportionated rosin ester, newtrex ester, petroleum resin such as C5/C9 through-stone oleoresin, aromatics through-stone oleoresin, αJia Jibenyixi, styrene/tackifying resins such as phenylethylene resin series such as αJia Jibenyixi multipolymer.They can use separately or also use more than 2 kinds.
In order to show high bounding force, the softening point of tackifying resin is preferably 50 ℃～150 ℃.
The use level of tackifying resin in the bonding agent of the present invention, can be according to the suitably selections such as kind of adherend, but cohesiveness reduces because if use level increases then, bad problem such as residual adhesive when having reprocessing, gross mass with respect to all solids composition that contains in the bonding agent, the use level of tackifying resin is preferably below the 25 quality %, more preferably below the 20 quality %, more preferably below the 10 quality %.
As the plastifier that can use as required in the bonding agent of the present invention, for example can enumerate, dibatyl phithalate, the phthalic acid di-n-octyl, phthalic acid two 2-Octyl Nitrites, phthalic acid two ester in the positive last of the ten Heavenly stems, phthalic acid ester classes such as phthalic acid two isodecyl esters, hexane diacid two 2-Octyl Nitrites, adipate classes such as di n octyl adipate, decanedioic acid two 2-Octyl Nitrites, sebacic acid esters such as n-butyl sebacate, fatty acid esters such as azelate such as azelaic acid 2-Octyl Nitrite, paraffinics such as chlorinated paraffin, alcohols such as polypropylene glycol, epoxidised soybean oil, epoxidation linseed wet goods epoxies polymeric plasticizer, tricresyl phosphate octyl group ester, phosphoric acid esters such as Triphenyl phosphate, phosphorous acid esters such as tricresyl phosphite phenylester, hexane diacid and 1, the ester oligomer classes such as carboxylate of 3-butylene glycol, poly-(methyl) n-butylacrylate, acrylic oligomers such as poly-(methyl) 2-EHA, polybutylene, polyisobutylene, polyisoprene, processing oil, the cycloalkane wet goods, they can use separately or also use more than 2 kinds.
The use level of the plastifier in the bonding agent of the present invention with respect to the gross mass of all solids composition that contains in the bonding agent, is preferably below the 25 quality %, more preferably below the 10 quality %.If the use level of plastifier cohesiveness at most reduces, bad problem such as residual adhesive when easily producing reprocessing.
As the above-mentioned composition in addition that can add as required in the bonding agent of the present invention, for example can enumerate, be used for further improving the antioxidant or the ultraviolet light absorber of weatherability, thermotolerance, inoxidizability, inorganic powder filling agents such as lime carbonate, titanium dioxide, mica, talcum, fibrous fillers such as glass fibre, organic reinforced fiber etc.In addition, in order to improve under high humility the cohesive with glass, can contain silane coupling agent.Further, as the compounding ingredient that is used for adhesive phase is given required function, can contain light diffusing agent, near infrared ray absorption, colorant, antistatic agent, electric conductivity imparting agent etc.
Pressure-sensitive adhesive for optical films of the present invention, for by chasing after variations such as distortion from base material or adherend, expansion, contraction, alleviate the stress that base material or adherend are applied and long-term performance goes out stable bounding force and permanance, when preferably under the frequency of 6.28rad/s, measuring the dynamic viscoelastic of bonding agent, and the energy storage elastic modulus under 23 ℃ [G ' (23 ℃)] be 1.0 * 10 5～8.0 * 10 5Energy storage elastic modulus under Pa and 90 ℃ [G ' (90 ℃)] be 7.0 * 10 4～6.0 * 10 5Pa, and more preferably above-mentioned energy storage elastic modulus [G ' (23 ℃)] be 2.0 * 10 5～8.0 * 10 5Pa and energy storage elastic modulus [G ' (90 ℃)] be 8.0 * 10 4～5.5 * 10 5Pa, and further preferred energy storage elastic modulus [G ' (23 ℃)] be 4.0 * 10 5～8.0 * 10 5Pa and energy storage elastic modulus [G ' (90 ℃)] be 2.0 * 10 5～5.5 * 10 5Pa.
Wherein, when under the frequency of 6.28rad/s, measuring dynamic viscoelastic in this instructions, above-mentioned 23 ℃ down energy storage elastic modulus [G ' (23 ℃)] and 90 ℃ under energy storage elastic modulus [G ' (90 ℃)] refer to the value that obtains with the method mensuration of putting down in writing among the following embodiment.
By the quality % of the weight-average molecular weight (Mw) of acrylic acid series triblock copolymer (I) and polymer blocks B, the addition that constitutes monomeric unit, various adjuvant (tackifying resin, plastifier etc.) are adjusted, can be simply and successfully obtain above-mentioned energy storage elastic modulus [G ' (23 ℃)] and energy storage elastic modulus [G ' (90 ℃)].
In addition, owing to, change each polymer ratio, can prepare and have the bonding agent of suitable dynamic viscoelastic, can easily make, provide the bonding agent that is fit to various blooming base materials by using multiple acrylic acid series triblock copolymer (I).Further, for the inequality that derives from raw material, the cooperation in the time of can adjusting the bonding agent cooperation is imperceptibly formed, thereby can supply with the extremely stable bonding agent of quality.
As the plastic material that uses in the blooming, for example can enumerate, polyethylene terephthalate (PET), triacetyl cellulose (TAC), polyvinyl alcohol (PVA) (PVA), polycarbonate, cycloolefin resinoid, styrene-methyl methacrylate copolymer resin (MS resin), acrylic resin, acrylic Acid UV resin etc., in order to show the function of blooming, they are separately used.For example, in polarization plates, use and on PVA, make the directed film that forms of dichromatism pigment (being mainly iodine) absorption as blooming; film strength lacks when only utilizing PVA; in order to suppress flexible under damp and hot, the thermal environment, as the effect of diaphragm, use usually at both sides applying TAC film.In addition, also have the polarization plates of having given phase difference function, be coated with discotic mesogenic this moment on the TAC as diaphragm, uses the phase retardation film that stretchings such as polycarbonate, cycloolefin resinoid are obtained to substitute the TAC that forms diaphragm in addition.Further, in prismatic lens, use on the PET film by acrylic Acid UV resin etc. and forms the prismatic lens that prism forms, use MS resin, polycarbonate in diffuser plate.And, as diffusion barrier, exist in the diffusion barrier that coating pearl layer forms on PET film, the polycarbonate membrane, implemented the diffusion barrier of surface working, contain the diffusion barrier of internal divergence agent etc.In addition, in light guide plate, exist special processing is carried out on the surface of acrylic panel, make from the luminous light guide plate in the even ground of the light of surface feeding sputtering etc., use the reflector plate that has utilized the PET film at the downside of this light guide plate.
Image display device is made of the layered product of above-mentioned multiple blooming usually.Go up or paste the bonding agent that uses in different types of blooming as blooming being pasted glass substrate etc., preferably can chase after and carry out bonding from the difference of the coefficient of thermal expansion between poor or different types of blooming of the coefficient of thermal expansion between blooming and the glass substrate (change in size that raises and cause along with temperature) (change in size that raises and cause along with temperature).In the blooming, particularly under the situation of polarization plates, by the PVA that stretches is applied thermal stress, polarization plates desires to return state originally (state before stretching), so might produce big contraction under heat condition.Therefore, the bonding agent that uses when polarization plates being pasted the bonding agent on the liquid crystal cell or pasting other blooming for polarization plates requires to relax for stress the following of the change in size that is caused.Further, when utilizing polarization plates, if to the polarization plates stress application, then produce stress birefrin (phase differential), lift-launch might produce the bad problem of optics inequality (the black phenomenon that spills white light when showing LCD at the image periphery) on LCD the time, under this situation, can reduce the optics inequality for the following of change in size by improving bonding agent usually.
Bonding agent of the present invention can use with the form of solvent-based adhesive or solid binder.
When making solvent-based adhesive, can prepare in the organic solvents such as toluene, ethyl acetate, butyl acetate, methyl ethyl ketone by acrylic acid series triblock copolymer (I) and other composition as required [acrylic acid series diblock copolymer (II), tackifying resin, plastifier, other one-tenth grade] for example are dissolved under lower temperature (being generally the temperature about 0～70 ℃).
In addition, when making solid binder, can be by using known kneading devices such as kneader, extruder, mixing mill, Banbury mixer, the common mixing in 100 ℃～250 ℃ temperature range prepares.
Wherein, bonding agent of the present invention preferably uses with the form of solvent-based adhesive, can not produce distortion or rotten, orientation, the residual stress etc. of base material, adherend, can not follow high temperature to heat and will approach, the uniform adhesive phase of thickness is formed on base material or the adherend.
When particularly being dissolved in the organic solvent as the bonding agent of the present invention of main body with acrylic acid series triblock copolymer (I), even under higher-solid concentration, also show low solution viscosity, even be dissolved in the toluene when forming solid component concentration and being the highly concentrated solution of 45 quality %, preferably measuring the solution viscosity that obtains with Brookfield viscometer under 25 ℃ temperature is 1000～4000mPas, more preferably 1500～3500mPas, 2000～3500mPas more preferably.Therefore, bonding agent of the present invention can be in the consumption that reduces organic solvent, form the solid component concentration ratio bonding agent of high solution-type (solid component concentration is the above solvent-based adhesives of 35 quality %) in the past, the solvent-based adhesive of this higher-solid, although the solid component concentration height, operability during coating or processability (omission of the reduction of drying load, the raising of coating speed, curing schedule etc.) excellence.
When bonding agent of the present invention is used as solvent-based adhesive, consider from aspects such as the coating of solvent-based adhesive, operability, processabilities, the total content of all solids composition of preferred acrylic acid series triblock copolymer (I) and the acrylic acid series diblock copolymer (II) that uses as required, tackifying resin, plastifier, other composition, quality with respect to solvent-based adhesive, be 30～60 quality %, particularly 35～55 quality %
As mentioned above, pressure-sensitive adhesive for optical films of the present invention is the pressure-sensitive adhesive for optical films of cross-linking type non-chemically.
Wherein, " cross-linking type non-chemically " refers in the manufacturing step at adhesive article (the preservation step of bonding agent, application step, drying steps, edging step, transportation step etc.), is not attended by the chemical crosslink reaction that covalent bond forms as having in the polymkeric substance of adhesive ingredients.
Blooming in the past is with the acrylic acid series polymeric compounds that uses in the acrylic adhesive, as described in patent documentation 1～3, usually with copolymerization such as acrylic acid, methacrylic acid, acrylic acid 2-hydroxy methacrylate, the own esters of acrylic acid 6-hydroxyl, have carboxyl, hydroxyl isoreactivity group.This blooming in the past with acrylic adhesive owing to only can not show the necessary cohesiveness of bonding agent when utilizing acrylic acid series polymeric compounds, usually (for example cooperate polyfunctional crosslinking chemical, isocyanate compound, epoxy compound, ethylene imine compound etc.), in the manufacturing step of adhesive article, make reactive group and crosslinking chemical in the polymkeric substance carry out chemical crosslink reaction and show cohesiveness.
Therewith relatively, pressure-sensitive adhesive for optical films of the present invention since in as the acrylic acid series triblock copolymer (I) of the main body of bonding agent physically pseudo-crosslinked of polymer blocks A1 and A2 formation, even do not carry out the blooming necessary chemical crosslinking of acrylic adhesive in the past, can show bond properties yet with sufficient permanance.
By making pressure-sensitive adhesive for optical films of the present invention be cross-linking type non-chemically, can from the manufacturing step of adhesive article, save the required time of chemical crosslink reaction, can significantly improve productivity.In addition, pressure-sensitive adhesive for optical films of the present invention has reactive functional group owing to there is no need to cooperate crosslinking chemical and not containing, so excellent storage stability can be with direct long preservation of bonding agent or the recycling that remains in when the manufacturing of adhesive optical film in the bonding agent groove.
Cross-linking type acryloid cement in the past at room temperature carries out cross-linking reaction owing to be two liquid system of host and crosslinking chemical mainly after two liquid are mixed, so if do not use then bonding rerum natura or coating characteristics to change after mixing immediately.
Further, blooming in the past is with in the acrylic adhesive, because above-mentioned cross-linking reaction is carried out in the preservation process of drying steps or goods, produce crosslinked inequality according to drying condition (temperature, air quantity, linear velocity etc.) or preservation condition (storage life, temperature etc.), exist the bond properties of goods to produce uneven bad problem, but non-chemically the pressure-sensitive adhesive for optical films of the present invention of cross-linking type can not produce this bad problem.
In addition, used the blooming or the blooming diaphragm of bonding agent of the present invention because bonding agent is cross-linking type non-chemically, bounding force through the time rising low, so even after sticking on the adherend for a long time, can residual adhesive etc. and can easily peel off yet.
When utilizing cross-linking type acryloid cement in the past, because crosslinking chemical and water reactions such as isocyanates are necessary binder solution is carried out strict water management.And, when blooming is polarization plates, most residual moisture or alcohols in the polarization plates, they might react with the crosslinking chemical in the cross-linking type acryloid cement, so there is crosslinked, the bonding rerum natura problem of unstable that can not stably carry out bonding agent.Therewith relatively, pressure-sensitive adhesive for optical films of the present invention there is no need binder solution or blooming base material are carried out strict water management owing to need not crosslinking chemical, has the stable high advantage of product property.
The pressure-sensitive adhesive for optical films of the application of the invention obtains having the adhesive optical film or the adhesive optical film diaphragm of the adhesive phase of the present invention that does not carry out chemical crosslinking.
Adhesive optical film and blooming diaphragm with pressure-sensitive adhesive for optical films layer of the present invention; have the bonding coat that one deck is at least formed by pressure-sensitive adhesive for optical films of the present invention by the blooming that in various image display devices such as liquid crystal indicator, PDP, organic EL display, Electronic Paper, uses or this blooming with part or all of the one or both sides of diaphragm, make without cross-linking step.As the blooming of this moment, for example can enumerating, polarizing coating, polarization plates, phase retardation film, visual angle amplification film, brightness improve film, antireflection film, prevent dazzling film, color filter, light guide plate, diffusion barrier, prismatic lens, electromagnetic shielding film, near-infrared absorption film, being compounded with the functional complex optical film of multiple optical function etc.In addition, as the blooming diaphragm, can enumerate the film that sticks in order to protect above-mentioned various blooming on this blooming.
Use the adhesive optical film and the blooming diaphragm of pressure-sensitive adhesive for optical films of the present invention; for example can by (i) above-mentioned blooming or blooming with diaphragm on the method for coating pressure-sensitive adhesive for optical films of the present invention, (ii) on the mold release film such as polyethylene terephthalate film that the demoulding was in advance handled, be coated with pressure-sensitive adhesive for optical films of the present invention, it is overlapped with diaphragm with blooming or blooming bonding coat is transferred to blooming or blooming waits with the method on the diaphragm and make.
Use the adhesive optical film and the blooming diaphragm of the pressure-sensitive adhesive for optical films manufacturing of the present invention of cross-linking type non-chemically; necessary annealing or curing are not disposed when not using the cross-linking type acryloid cement; and can be directly as the goods listing that can paste on liquid crystal panel or other the adherend, the productivity excellence.
Use adhesive optical film that pressure-sensitive adhesive for optical films of the present invention forms and blooming to be with the re-workability excellence of diaphragm because, since do not carry out functional group or crosslinking chemical through the time chemical crosslink reaction, bounding force through the time variation little.The blooming in the past that contains crosslinking chemical carries out chemical crosslink reaction with in the acrylic adhesive in the preservation process of goods, bounding force rises, and is difficult to reprocess.
Require in the purposes of re-workability, 180 ° of peel adhesion when reprocessing operation are preferably 0.05～20N/25mm usually, more preferably 0.1～15N/25mm, more preferably 3～10N/25mm.Pressure-sensitive adhesive for optical films of the present invention is even also keep above-mentioned preferred 180 ° of peel adhesion after thermal treatment.
Embodiment
Wait by the following examples the present invention is carried out more specific description, but the present invention is not limited by following embodiment.
Acrylic acid series triblock copolymer that uses in embodiment and the comparative example and acrylic acid series diblock copolymer use the chemical reagent that obtains by the dry purifying of conventional method, and be synthetic by synthesis example shown below.
The weight-average molecular weight (Mw) of acrylic acid series triblock copolymer that is synthesized in addition, and acrylic acid series diblock copolymer, number-average molecular weight (Mn), molecular weight distribution (Mw/Mn), form (the positive butyl ester block of polyacrylic acid in acrylic acid series triblock copolymer and the acrylic acid series diblock copolymer contain ratio), normality between the polymethylmethacrylablock block in the triblock copolymer [stereospecific (rr)], the glass transition temperature of each polymer blocks, the polymerisation conversion that adds monomer, the energy storage elastic modulus of bonding agent, the solution viscosity of bonding agent, the bounding force of bonding agent and adhesive residue (are pasted the bounding force and the adhesive residue at initial stage, bounding force after the thermal treatment and adhesive residue, bounding force and adhesive residue after autoclave is handled, bounding force and adhesive residue after autoclave processing and the thermal treatment), the mensuration of the shear adhesion fail temperature (SAFT) of the confining force of adhesive optical film test (creep test) and bonding agent or estimate following carrying out.
(1) weight-average molecular weight of segmented copolymer (Mw) and number-average molecular weight (Mn):
Use is dissolved in segmented copolymer the solution that obtains in the tetrahydrofuran, use following apparatus and condition, by gel permeation chromatography (GPC), the weight-average molecular weight (Mw) and the number-average molecular weight (Mn) of acrylic acid series triblock copolymer and acrylic acid series diblock copolymer are measured.
-device: TOSOH society system gel permeation chromatography " HLC-8020 "
-chromatographic column: TSKgel GMHXL, G4000HXL and the G5000HXL of TOSOH society system are connected in series
-eluant, eluent: tetrahydrofuran
-eluant, eluent flow: 1.0ml/ minute
-chromatogram column temperature: 40 ℃
-detection method: differential refraction rate (RI)
-typical curve: use polystyrene standard to make
(2) molecular weight distribution of segmented copolymer (Mw/Mn):
With the value of the weight-average molecular weight (Mw) of the acrylic acid series triblock copolymer that obtains in above-mentioned (1) or acrylic acid series diblock copolymer value, try to achieve the molecular weight distribution (Mw/Mn) of acrylic acid series triblock copolymer and acrylic acid series diblock copolymer respectively divided by number-average molecular weight (Mn).
(3) composition of segmented copolymer:
Acrylic acid series triblock copolymer or acrylic acid series diblock copolymer are dissolved in the deuterochloroform, use Jeol Ltd.'s system nuclear magnetic resonance device (" JNM-LA400 "), use deuterochloroform as solvent, by proton magnetic resonance (PMR) ( 1H-NMR) optical spectroscopy is measured the composition (polymethylmethacrylablock block in acrylic acid series triblock copolymer and the acrylic acid series diblock copolymer and the positive butyl ester block of polyacrylic acid contain ratio) of segmented copolymer.
At this moment, exist 1In the H-NMR spectrum, near the signal 3.6ppm and the 4.0ppm belongs to the ester group (O-C of methyl methacrylate units respectively H 3) and the ester group (O-C of n-butyl acrylate unit H 2-CH 2-CH 2-CH 3), try to achieve the content of copolymer composition by the ratio of its integrated value.
(4) polymethylmethacrylablock block in the acrylic acid series triblock copolymer between normality [stereospecific (rr)]:
The acrylic acid series triblock copolymer is dissolved in the deuterochloroform, use Jeol Ltd.'s system nuclear magnetic resonance device (" JNM-LA400 "), try to achieve methylmethacrylate polymer block (polymer blocks A1 and A2) in the acrylic acid series triblock copolymer between normality [stereospecific (rr)].
At this moment, exist 13In the C-NMR spectrum, near the signal 44.5ppm, 44.8ppm and the 45.5ppm belongs to the quaternary carbon of polymethylmethacrylablock block, corresponds respectively to stereospecific rr, mr and mm, tries to achieve stereospecific rr by the ratio of its integrated value.And stereospecific also can pass through 1The H-NMR method is tried to achieve.In the segmented copolymer that uses in embodiments of the invention and the comparative example, owing to use 1The H-NMR method is difficult to separate from the signal of polymethylmethacrylate and signal from the positive butyl ester of polyacrylic acid, and employing is passed through 13The analysis that the C-NMR method is carried out.
(5) glass transition temperature of each polymer blocks (Tg):
Using the DSC determinator (DSC-822) of METTLER-TOLEDO corporate system, is to carry out DSC under 10 ℃/minute the condition to measure and obtain curve at programming rate, in this curve, extrapolation is begun temperature (Tgi) as glass transition temperature (Tg).
(6) polymerisation conversion of adding monomer:
Collect the part of reactant liquor of the formation reaction ending phase of each polymer blocks, adopt following device and condition, the amount of residual monomer in the assaying reaction liquid is tried to achieve the polymerization adding rate of monomer.
-device: Shimadzu Seisakusho Ltd.'s system gas chromatography " GC-14A "
-chromatographic column: GL Sciences Inc. system " INERT CAP 1 " [internal diameter 0.25mm * long 60m, thickness (df) 0.4 μ m]
-analysis condition: inject ℃/minute (keeping 0 minute) → 15, (injection) 300 ℃, 300 ℃, 60 ℃ (keeping 0 minute) → 5 of detecting device (detecter) ℃/minute → 10 ℃/minute → 300 ℃ (keeping 2 minutes)
(7) the energy storage elastic modulus of bonding agent:
(i) bonding agent of following embodiment or comparative example is dissolved in after the preparation solid component concentration is the binder solution of 30 quality % in the toluene, this solution is injected in the case made from processing release paper (base material).Then, after at room temperature air-dry 24 hours,, make the sheet of the thickness of adhesive phase for about 1mm 60 ℃ of following vacuum drying 24 hours, this sheet stamping-out is become the circle of diameter 8mm after, peel off base material manufacturing test film.
(ii) use test film of making in above-mentioned (i), adopt following apparatus and condition, measure the dynamic viscoelastic temperature dispersion, the value of the energy storage elastic modulus under 23 ℃ and the 90 ℃ of temperature (G ') is counted respectively " G ' (23 ℃) " and " G ' (90 ℃) ".
-device: Rhemetric Scientific corporate system " Advanced Rheometric ExpansionSystem "
-parallel-plate: diameter 8mm
-frequency: 6.28rad/s
-mensuration temperature range :-50 ℃～250 ℃
-programming rate: 3 ℃/minute
-deformation: 0.05% (50 ℃～-37 ℃), 1.0% (37 ℃～-15 ℃), 5.0% (15 ℃～250 ℃)
(8) solution viscosity of bonding agent:
Following embodiment or bonding agent be dissolved in the preparation solid component concentration is the binder solution of 45 quality % in the toluene, use Brookfield viscometer (Co., Ltd.'s Tokyo gauge is made made " BL type viscosity meter ") to measure the viscosity of this binder solution under 25 ℃ of temperature.
(9) bounding force of bonding agent and adhesive residue:
(i) with the adhesive optical film that contains demoulding polyethylene terephthalate film/bonding agent/polyethylene terephthalate film base material made in following embodiment or the comparative example [below be referred to as " adhesive optical film (α) "], or the adhesive optical film (adhesion type polarization plates) [below be referred to as " adhesive optical film (β) "] that contains demoulding polyethylene terephthalate film/bonding agent/polarization plates is cut into the size of width * length=25mm * 200mm, the manufacturing test film [and, in following embodiment and comparative example, sometimes adhesive optical film (α) and adhesive optical film (β) are referred to as " adhesive optical film "].
(ii) paste the initial stage bounding force and the adhesive residue of (non-thermal treatment):
(a) demoulding PET film on a surface of the test film of manufacturing in above-mentioned (i) is peeled off, paste on the glass plate or polycarbonate system flat board as adherend, the roller that uses 2kg is with the speed of 10mm/ second on adhesive optical film reciprocal 2 times, paste, after placing 24 hours under 23 ℃ of temperature, humidity 50%RH, the atmospheric pressure, then, measure 180 ° of peel adhesion with 300mm/ minute peeling rate according to JIS Z0237.
(b) by visualization residual adhesive whether on glass-board surface behind the determination test of 180 ° of peel adhesion of above-mentioned (a) or polycarbonate system platen surface, with the average evaluation of residual adhesive is " having adhesive residue ", and residual adhesive not, the average evaluation successfully peeled off are " adhesive-free is residual ".
(iii) bounding force after the thermal treatment and adhesive residue:
(a) demoulding PET film on a surface of the test film of manufacturing in above-mentioned (i) is peeled off, paste on the glass plate or polycarbonate system flat board as adherend, the roller that uses 2kg is with the speed of 10mm/ second on adhesive optical film reciprocal 2 times, paste, after placement was heat-treated in 15 hours in the hot-air oven of 70 ℃ of temperature, further under the atmospheric pressure of 23 ℃ of temperature, humidity 50%RH, place and carried out damping in 1 hour, according to JIS Z0237, measure 180 ° of peel adhesion with 300mm/ minute peeling rate.
(b) by visualization residual adhesive whether on glass-board surface behind the determination test of 180 ° of peel adhesion of above-mentioned (a) or polycarbonate system platen surface, with the average evaluation of residual adhesive is " having adhesive residue ", and residual adhesive not, the average evaluation successfully peeled off are " adhesive-free is residual ".
Bounding force and adhesive residue after (iv) autoclave is handled:
(a) demoulding PET film on a surface of the test film of manufacturing in above-mentioned (i) is peeled off, paste on the glass plate or polycarbonate system flat board as adherend, the roller that uses 2kg is with the speed of 10mm/ second on adhesive optical film reciprocal 2 times, paste, be to place under the condition of 5 atmospheric pressure (0.5MPa) to carry out in 15 minutes after autoclave handles at 50 ℃ of temperature, pressure, further under the atmospheric pressure of 23 ℃ of temperature, humidity 50%RH, place and carried out damping in 1 hour, according to JISZ0237, measure 180 ° of peel adhesion with 300mm/ minute peeling rate.
(b) by visualization residual adhesive whether on glass-board surface behind the determination test of 180 ° of peel adhesion of above-mentioned (a) or polycarbonate system platen surface, with the average evaluation of residual adhesive is " having adhesive residue ", and residual adhesive not, the average evaluation successfully peeled off are " adhesive-free is residual ".
(v) autoclave handle and thermal treatment after bounding force and adhesive residue:
(a) demoulding PET film on a surface of the test film of manufacturing in above-mentioned (i) is peeled off, paste on the glass plate or polycarbonate system flat board as adherend, the roller that uses 2kg is with the speed of 10mm/ second on adhesive optical film reciprocal 2 times, paste, 50 ℃ of temperature, pressure is to place under the condition of 5 atmospheric pressure (0.5MPa) to carry out in 15 minutes after autoclave handles, in the hot-air oven of 70 ℃ of temperature, place and heat-treated in 15 hours, then 23 ℃ of temperature, the atmospheric pressure of humidity 50%RH is placed down and was carried out damping in 1 hour, according to JIS Z0237, measure 180 ° of peel adhesion with 300mm/ minute peeling rate.
(b) by visualization residual adhesive whether on glass-board surface behind the determination test of 180 ° of peel adhesion of above-mentioned (a) or polycarbonate system platen surface, with the average evaluation of residual adhesive is " having adhesive residue ", and residual adhesive not, the average evaluation successfully peeled off are " adhesive-free is residual ".
(10) confining force of adhesive optical film test (creep test):
(i) adhesive optical film (α) (layered product that contains demoulding PET film/bonding agent/PET film base material) or the adhesive optical film of making in following embodiment or the comparative example (β) (layered product that contains demoulding PET film/bonding agent/polarization plates) is cut into width 25mm, length 40mm, makes test film.
The part of the residual installation counterweight of making in (ii) above-mentioned (i) of test film, the demoulding PET film on a surface is peeled off, with Width 25mm (for the right angle orientation that is oriented of load), longitudinal direction 10mm (with the load towards equidirectional) paste on the glass plate or polycarbonate system flat board as adherend, the counterweight of 1kg is installed on this test film, under 90 ℃ of temperature, according to JISZ0237, measure after 30 minutes, after 60 minutes or after 1000 minutes the position deviation of test film the time, from glass plate or the dull and stereotyped disbonded test sheet of polycarbonate system, measure the time that counterweight falls.
Then, according to the metewand shown in the following table 1, the permanance (bonding confining force) of bonding agent is marked.
This test is the test that is used to investigate the permanance of bonding agent, the position deviation of no test film, and the long more bonding agent permanance that then shows of time before test film comes off in addition is excellent more.
[table 1]
[evaluation content of creep test]
Figure GSB00000369848800301
(11) the shear adhesion fail temperature (SAFT) of bonding agent:
Measure according to ASTM D4498.
Specifically, adhesive optical film (α) (layered product that contains demoulding PET film/bonding agent/PET film base material) or the adhesive optical film (β) (layered product that contains demoulding PET film/bonding agent/polarization plates) made in following embodiment or the comparative example are cut into width 25mm, length 60mm, make test film, the part of residual installation counterweight, the demoulding PET film on a surface is peeled off, square size with 25mm * 25mm pastes on the glass plate, with it 25 ℃ of temperature, preserve after 24 hours under the condition of humidity 50%RH, put into 40 ℃ baking oven, the counterweight of 500g is installed at the central portion on one side of test film, with 0.5 ℃/minute programming rate temperature of oven is warming up to 220 ℃ from 40 ℃ then, the temperature of record counterweight when test film comes off.
This test is permanance and the stable on heating test that is used to investigate bonding agent, and the permanance and the thermotolerance of the high more then bonding agent of the temperature when counterweight comes off are excellent more, and expression is adapted at using under the hot conditions.
" synthesis example 1 " [synthesizing of acrylic acid series triblock copolymer (Ia-1)]
(1) additional tripartite cock (three-way cock) on the three-neck flask of 2L, and with inside with nitrogen replacement after, at room temperature add toluene 868g, 1,2-dimethoxy-ethane 43.4g, contain isobutyl two (2,6-di-t-butyl-4-methylphenoxy) the toluene solution 60.0g of aluminium 40.2mmol further adds and contains the cyclohexane of s-butyl lithium 5.00mmol and the mixed solution 2.89g of normal hexane.Then, to wherein adding methyl methacrylate 35.9g.It is yellow that reactant liquor is initially, and becomes colorless but at room temperature stir after 60 minutes.At this moment, the Polymerization of Methyl conversion ratio is more than 99.9%.Then, the internal temperature of polymer fluid is cooled to-30 ℃,, drips and finish the back and stirred 5 minutes down at-30 ℃ with 2 hours positive butyl ester 240g of dropwise addition of acrylic acid.At this moment, the polymerisation conversion of n-butyl acrylate is more than 99.9%.Further, after wherein adding methyl methacrylate 35.9g, at room temperature stirring a night, add methyl alcohol 3.50g and stop polyreaction.At this moment, the Polymerization of Methyl conversion ratio is more than 99.9%.The reactant liquor that obtains is injected in the 15kg methyl alcohol, separates out white depositions.Then,, carry out drying, obtain acrylic acid series triblock copolymer [acrylic acid series triblock copolymer (Ia-1)] 308g thus by the filtered and recycled white depositions.
(2) result who measures by said method is as follows: the acrylic acid series triblock copolymer (Ia-1) that obtains in above-mentioned (1) is for containing the triblock copolymer of polymethylmethacrylate (PMMA)-positive butyl ester of polyacrylic acid (PnBA)-polymethylmethacrylate (PMMA), weight-average molecular weight (Mw) is 73000, number-average molecular weight (Mn) is 65200, and molecular weight distribution (Mw/Mn) is 1.12.
In addition, the mass ratio of each polymer blocks in the acrylic acid series triblock copolymer (Ia-1) is PMMA (11.5 quality %)-PnBA (77.0 quality %)-PMMA (11.5 quality %), and the content of PnBA block is 77.0 quality %.
Further, the glass transition temperature of the PMMA block in the acrylic acid series triblock copolymer (Ia-1) is 100.3 ℃, and the glass transition temperature of PnBA block is-46.5 ℃.
In addition, the PMMA block between normality [stereospecific (rr)] be 67.3%.
" synthesis example 2 " [synthesizing of acrylic acid series triblock copolymer (Ia-2)]
(1) additional tripartite cock on the three-neck flask of 2L, with inside with nitrogen replacement after, at room temperature add toluene 868g, 1,2-dimethoxy-ethane 43.4g, contain isobutyl two (2,6-di-t-butyl-4-methylphenoxy) the toluene solution 60.0g of aluminium 40.2mmol further adds and contains the cyclohexane of s-butyl lithium 6.37mmol and the mixed solution 3.68g of normal hexane.Then, to wherein adding methyl methacrylate 49.9g.It is yellow that reactant liquor is initially, and becomes colorless but at room temperature stir after 60 minutes.At this moment, the Polymerization of Methyl conversion ratio is more than 99.9%.Then, the internal temperature of polymer fluid is cooled to-30 ℃,, drips and finish the back and stirred 5 minutes down at-30 ℃ with 2 hours positive butyl ester 212g of dropwise addition of acrylic acid.At this moment, the polymerisation conversion of n-butyl acrylate is more than 99.9%.Further, after wherein adding methyl methacrylate 49.9g, at room temperature stirring a night, add methyl alcohol 3.50g and stop polyreaction.At this moment, the Polymerization of Methyl conversion ratio is more than 99.9%.The reactant liquor that obtains is injected in the 15kg methyl alcohol, separates out white depositions.Then,, carry out drying, obtain triblock copolymer [acrylic acid series triblock copolymer (Ia-2)] 310g thus by the filtered and recycled white depositions.
(2) result who measures by said method is as follows: the acrylic acid series triblock copolymer (Ia-2) that obtains in above-mentioned (1) is the triblock copolymer that contains PMMA-PnBA-PMMA, weight-average molecular weight (Mw) is 63000, number-average molecular weight (Mn) is 50000, and molecular weight distribution (Mw/Mn) is 1.26.
In addition, the mass ratio of each block in the acrylic acid series triblock copolymer (Ia-2) is PMMA (16.0 quality %)-PnBA (68.0 quality %)-PMMA (16.0 quality %), and the content of PnBA block is 68.0 quality %.
Further, the glass transition temperature of the PMMA block in the acrylic acid series triblock copolymer (Ia-2) is 101.8 ℃, and the glass transition temperature of PnBA block is-44.6 ℃.
In addition, the PMMA block between normality [stereospecific (rr)] be 70.5%.
" synthesis example 3～6 " [acrylic acid series triblock copolymer (Ia-3) and (Ib-1)～(Ib-3) synthetic]
Carry out with embodiment 1 in (1) same operation, the acrylic acid series triblock copolymer (Ia-3) of normality between synthetic respectively glass transition temperature with the weight-average molecular weight shown in the following table 2 (Mw), molecular weight distribution (Mw/Mn), PnBA block content, each polymer blocks and PMMA, (Ib-1), (Ib-2) and (Ib-3).
" synthesis example 7 " [synthesizing of acrylic acid series diblock copolymer (IIa)]
(1) additional tripartite cock on the three-neck flask of 2L, with inside with nitrogen replacement after, at room temperature add toluene 868g, 1,2-dimethoxy-ethane 43.4g, contain isobutyl two (2,6-di-t-butyl-4-methylphenoxy) the toluene solution 30.0g of aluminium 20.1mmol further adds and contains the cyclohexane of s-butyl lithium 4.30mmol and the mixed solution 3.31g of normal hexane.Then, to wherein adding methyl methacrylate 21.5g.It is yellow that reactant liquor is initially, and becomes colorless but at room temperature stir after 60 minutes.At this moment, the Polymerization of Methyl conversion ratio is more than 99.9%.Then, the internal temperature of polymer fluid is cooled to-30 ℃, with 2 hours positive butyl ester 291g of dropwise addition of acrylic acid, drip finish the back-30 ℃ stir 5 minutes down after, add methyl alcohol 3.5g and stop polyreaction.At this moment, the polymerisation conversion of n-butyl acrylate is more than 99.9%.Then, the reactant liquor that obtains is injected in the 15kg methyl alcohol, makes the colorless oil sedimentation.Behind the decant, carry out drying, obtain acrylic acid series diblock copolymer [acrylic acid series diblock copolymer (IIa)] 295g thus.
(2) result who measures by said method is, the acrylic acid series diblock copolymer (IIa) that obtains in above-mentioned (1) is the diblock copolymer that contains PMMA-PnBA, weight-average molecular weight (Mw) is 92000, and number-average molecular weight (Mn) is 76000, and molecular weight distribution (Mw/Mn) is 1.21.
In addition, the mass ratio of each block in the acrylic acid series diblock copolymer (IIa) is PMMA (6.9 quality %)-PnBA (93.1 quality %).
The acrylic acid series triblock copolymer (Ia-1)～(Ia-3) that obtains in the above-mentioned synthesis example 1～6 and (Ib-1)～(Ib-3) and the content of the acrylic acid series diblock copolymer (IIa) that obtains in the synthesis example 7 be recorded in the following table 2.
[table 2]
Figure GSB00000369848800341
1) structure of segmented copolymer:
S1：PMMA-PnBA-PMMA
S2：PMMA-PnBA
2) weight-average molecular weight of segmented copolymer integral body (Mw)
3) molecular weight distribution of segmented copolymer (Mw/Mn)
4) content of the PnBa block among triblock copolymer A1-B-A2 or the diblock copolymer C-D
5) the PMMA block among the triblock copolymer A1-B-A2 between normality [stereospecific (rr)]
" embodiment 1 "
(1) uses acrylic acid series triblock copolymer (Ia-1) the preparation pressure-sensitive adhesive for optical films that obtains in the synthesis example 1 separately.
Measure the energy storage elastic modulus [G ' (23 ℃)] of the bonding agent of this embodiment 1 and energy storage elastic modulus [G ' (90 ℃)] by said method, the result is shown in following table 3.
In addition, measure the solution viscosity of the bonding agent of this embodiment 1 by said method, the result is shown in following table 3.
(2) acrylic acid series triblock copolymer (Ia-1) is dissolved in the toluene, the preparation solid component concentration is the binder solution of 30 quality %, it is coated on the polyethylene terephthalate film (thickness 50 μ m), after under 60 ℃ dry 10 minutes, cover the bonding agent face with demoulding polyethylene terephthalate film (thickness 38 μ m), make the adhesive optical film (α) that contains demoulding PET film/bonding agent/PET base material film.
(3) use adhesive optical film (α) of making in above-mentioned (2), measure or estimate various rerum naturas by said method, the result is shown in following table 3.
" embodiment 2 "
(1) the acrylic acid series diblock copolymer (IIa) that obtains in the acrylic acid series triblock copolymer (Ia-2) that obtains in the synthesis example 2 and the synthesis example 7 is dissolved in 85: 15 mass ratio to make solid constituent in the toluene be 45 quality %, the preparation pressure-sensitive adhesive for optical films.
Measure the energy storage elastic modulus [G ' (23 ℃)] of this bonding agent and energy storage elastic modulus [G ' (90 ℃)] and solution viscosity by said method, the result is shown in following table 3.
(2) be the binder solution of 30 quality % except using the bonding agent that will obtain in above-mentioned (1) with the solid component concentration that dilution with toluene prepares, similarly make adhesive optical film (α) (layered product that contains demoulding PET film/bonding agent/PET film base material) with embodiment 1 (2), measure or estimate various rerum naturas by said method, the result is shown in following table 3.
" embodiment 3 "
(1) the acrylic acid series diblock copolymer (IIa) that obtains in the acrylic acid series triblock copolymer (Ia-2) that obtains in the synthesis example 2 and the synthesis example 7 is dissolved in 85: 15 mass ratio to make solid constituent in the toluene be 45 quality %, the preparation pressure-sensitive adhesive for optical films.
Measure the energy storage elastic modulus [G ' (23 ℃)] of this bonding agent and energy storage elastic modulus [G ' (90 ℃)] and solution viscosity by said method, the result is shown in following table 3.
(2) with the bonding agent dilution with toluene that obtains in above-mentioned (1), the preparation solid component concentration is the binder solution of 30 quality %, after being coated on it on polyethylene terephthalate film (thickness 38 μ m) that has carried out demoulding processing, drying is 10 minutes under 60 ℃, be formed on the film that has adhesive phase on the demoulding polyethylene terephthalate film, it is fitted on the commercially available polarization plates with laminating machine, make adhesive optical film (β) (layered product that contains demoulding PET film/bonding agent/polarization plates).
(3) use adhesive optical film (β) of making in above-mentioned (2), measure or estimate various rerum naturas by said method, the result is shown in following table 3.
" implementing side 4 "
(1) the acrylic acid series diblock copolymer (IIa) that obtains in the acrylic acid series triblock copolymer (Ia-3) that obtains in the synthesis example 3, the synthesis example 7 and tackifying resin (Arakawa Chemical Industries, Ltd.'s system " KE311 ", special rosin ester resin) are dissolved in 85: 5: 10 mass ratioes to make solid constituent in the toluene be 45 quality %, the preparation pressure-sensitive adhesive for optical films.
Measure the energy storage elastic modulus [G ' (23 ℃)] of this bonding agent and energy storage elastic modulus [G ' (90 ℃)] and solution viscosity by said method, the result is shown in following table 3.
(2) the bonding agent that obtains in above-mentioned except using (1), similarly make adhesive optical film (β) (layered product that contains demoulding PET film/bonding agent/polarization plates) with embodiment 3 (2), measure or estimate various rerum naturas by said method, the result is shown in following table 3.
" comparative example 1 "
(1) the acrylic acid series diblock copolymer (IIa) that obtains in the acrylic acid series triblock copolymer (Ia-1) that obtains in the synthesis example 1, the synthesis example 7 and tackifying resin (Arakawa Chemical Industries, Ltd.'s system " KE311 ", special rosin ester resin) are dissolved in 53: 5: 42 mass ratioes to make solid constituent in the toluene be 45 quality %, the preparation pressure-sensitive adhesive for optical films.
Measure the energy storage elastic modulus [G ' (23 ℃)] of this bonding agent and energy storage elastic modulus [G ' (90 ℃)] and solution viscosity by said method, the result is shown in following table 3.
(2) the bonding agent that obtains in above-mentioned except using (1), similarly make adhesive optical film (β) with embodiment 3 (2), measure or estimate various rerum naturas by said method, the result is shown in following table 3.
" embodiment 5～9 and comparative example 2 "
(1) with a kind or 2 kinds in the acrylic acid series triblock copolymer (Ib-2) that obtains in the acrylic acid series triblock copolymer (Ib-1) that obtains in the acrylic acid series triblock copolymer (Ia-1) that obtains in the synthesis example 1, the synthesis example 4 and the synthesis example 5, and the acrylic acid series diblock copolymer (IIa) that obtains in the synthesis example 7 is dissolved in the mass ratio shown in the following table 4 that to make solid constituent in the toluene be 45 quality %, the preparation pressure-sensitive adhesive for optical films.
Measure the energy storage elastic modulus [G ' (23 ℃)] of the bonding agent obtain thus and energy storage elastic modulus [G ' (90 ℃)] and solution viscosity by said method, the result is shown in following table 4.
(2) each bonding agent that obtains in above-mentioned except using (1), similarly make adhesive optical film (β) (layered product that contains demoulding PET film/bonding agent/polarization plates) with embodiment 3 (2), measure or estimate various rerum naturas by said method, the result is shown in following table 4.
" embodiment 10～13 "
(1) 2 kinds in the acrylic acid series triblock copolymer (Ib-3) that obtains in the acrylic acid series triblock copolymer (Ib-1) that obtains in the acrylic acid series triblock copolymer (Ia-2) that obtains in the synthesis example 2, the synthesis example 4 and the synthesis example 6 or 3 kinds are dissolved in the mass ratio shown in the following table 5 to make solid constituent in the toluene be 45 quality %, the preparation pressure-sensitive adhesive for optical films.
Measure the energy storage elastic modulus [G ' (23 ℃)] of the bonding agent obtain thus and energy storage elastic modulus [G ' (90 ℃)] and solution viscosity by said method, the result is shown in following table 5.
(2) each bonding agent that obtains in above-mentioned except using (1), similarly make adhesive optical film (α) (layered product that contains demoulding PET film/bonding agent/PET base material film) (embodiment 10 and embodiment 12) with embodiment 1 (2), or similarly make adhesive optical film (β) (layered product that contains demoulding PET film/bonding agent/polarization plates) (embodiment 11 and embodiment 13) with embodiment 3 (2), measure or estimate various rerum naturas by said method, the result is shown in following table 5.
[table 3]
1) solution viscosity of bonding agent: solid component concentration is the toluene solution (25 ℃) of 45 quality %
2) kind of adhesive optical film:
α: adhesive optical film (α) (layered product that contains demoulding PET film/bonding agent/PET film base material)
β: adhesive optical film (β) (layered product that contains demoulding PET film/bonding agent/polarization plates)
3) PC plate: polycarbonate flat board
[table 4]
Figure GSB00000369848800391
1) solution viscosity of bonding agent: the toluene solution of solid component concentration 45 quality % (25 ℃)
2) kind of adhesive optical film:
β: adhesive optical film (β) (layered product that contains demoulding PET film/bonding agent/polarization plates)
[table 5]
Figure GSB00000369848800401
1) solution viscosity of bonding agent: solid component concentration is the toluene solution (25 ℃) of 45 quality %
2) kind of adhesive optical film:
α: adhesive optical film (α) (layered product that contains demoulding PET film/bonding agent/PET film base material)
β: adhesive optical film (β) (layered product that contains demoulding PET film/bonding agent/polarization plates)
By the result of above-mentioned table 3～table 5 as can be known, the pressure-sensitive adhesive for optical films of embodiment 1～13 by contain with the ratio more than the 60 quality % of contained all solids composition in the bonding agent acrylic acid series triblock copolymer (Ia-1)～(Ia-3) that possesses above-mentioned condition (E1)～(E4) and (Ib-1)～(Ib-3) in a kind, 2 kinds or 3 kinds, energy storage elastic modulus [G ' (23 ℃)] is 1.0 * 10 5～8.0 * 10 5In the scope of Pa and energy storage elastic modulus [G ' (90 ℃)] 7.0 * 10 4～6.0 * 10 5In the scope of Pa, good to the following that the distortion of base material, adherend, expansion, contraction etc. change, reduce stress to base material, adherend, can bring into play more stable bounding force and permanance for a long time.
Further, use adhesive optical film (α) (layered product that contains demoulding PET film/bonding agent/PET base material film) that the bonding agent of this embodiment 1～13 makes and adhesive optical film (β) (layered product that contains demoulding PET film/bonding agent/polarization plates) after stickup initial stage, the thermal treatment, autoclave handles afterwards, all have suitable bounding force after autoclave and the thermal treatment (is generally 0.05～20N/25mm), adhesive-free is residual when peeling off, the re-workability excellence.
And, the bonding agent of embodiment 1～13 is in creep test, even the test film [test film of choosing from adhesive optical film (α) or adhesive optical film (β)] that sticks on after 60 minutes on glass plate or the polycarbonate flat board can not depart from or fall, excellent in te pins of durability, and the SAFT height, be more than 151 ℃, permanance and excellent heat resistance.
Particularly in the pressure-sensitive adhesive for optical films of embodiment 7 and embodiment 10～13, by being to be 100000～300000 acrylic acid series triblock copolymer (Ib) [acrylic acid series triblock copolymer (Ib-1) more than 50000 and less than 100000 acrylic acid series triblock copolymer (Ia) [acrylic acid series triblock copolymer (Ia-2)] and weight-average molecular weight (Mw) with weight-average molecular weight (Mw), or (Ib-1) and (Ib-3)] with acrylic acid series triblock copolymer (Ia): the ratio of acrylic acid series triblock copolymer (Ib)=45: 55～75: 25 (mass ratio) uses, in creep test, even the test film [test film of choosing from adhesive optical film (α) or adhesive optical film (β)] that sticks on after 1000 minutes on glass plate or the polycarbonate system flat board can not fall, and SAFT height, be more than 163 ℃, permanance and thermotolerance are extremely excellent.
Therewith relatively, the pressure-sensitive adhesive for optical films of comparative example 1 and comparative example 2 contains acrylic acid series triblock copolymer (I), but its contain ratio with respect to all solids composition of pressure-sensitive adhesive for optical films less than 60 quality %, the following that causes distortion, expansion, contraction etc. to base material, adherend to change is poor.
And, use adhesion type polarization plates (demoulding PET/ bonding agent/polarization plates) that the bonding agent of comparative example 1 and 2 makes after stickup initial stage, the thermal treatment, the bounding force of autoclave after handling back, autoclave and thermal treatment be too high, have adhesive residue when peeling off in addition, re-workability is poor.
Further, the bonding agent of comparative example 1 and comparative example 2, in creep test, the test film [test film of choosing from adhesion type polarization plates (demoulding PET/ bonding agent/polarization plates)] that sticks on glass plate or the polycarbonate system flat board fell after 1 minute very soon, poor durability, and the SAFT temperature is low, be 121 ℃ or 125 ℃, permanance and poor heat resistance.
Industrial applicibility
Pressure-sensitive adhesive for optical films of the present invention is cross-linking type non-chemically, need not chemical crosslinking processes, do not show high cohesiveness even do not carry out the chemical crosslinking processing yet, has excellent re-workability, adhesion characteristic, heat resistance, durability, and when being dissolved in the adhesive of making solution-type in the organic solvent, even owing under high concentration, also show low solution viscosity, so can reduce the consumption of organic solvent, and form solid component concentration than in the past high solvent-based adhesive, can reduce the deterioration of operating environment, the problem of environmental pollution, the solvent that reduces after being coated with is removed the required time of step, heat energy etc.
Particularly among the present invention, as acrylic acid series triblock copolymer (I), be more than 50000 and less than 100000 aforesaid propylene acid to be that triblock copolymer (Ia) and weight average molecular weight (Mw) are that to be triblock copolymer (Ib) cooperate the pressure-sensitive adhesive for optical films that forms can simpler and successfully adjust bonding rerum natura (bonding force with 45: 55～75: 25 mass ratio for 100000～300000 aforesaid propylene acid with weight average molecular weight (Mw), creep etc.), volume rerum natura (dynamic viscoelastic etc.) etc., and because durability, heat resistance and more excellent to the following of base material distortion industrially is exceedingly useful as pressure-sensitive adhesive for optical films.

Claims (20)

1. the pressure-sensitive adhesive for optical films of cross-linking type non-chemically, it is characterized in that, based on the gross mass of all solids composition that contains in the bonding agent, contain with the ratio more than the 60 quality % possess following condition (E1), (E2), (E3) and acrylic acid series triblock copolymer (I) (E4)
Zero acrylic acid series triblock copolymer (I):
(E1) the acrylic acid series triblock copolymer shown in the following general formula (1),
A1-B-A2(1)
In the formula, A1 and A2 represent independently that respectively glass transition temperature is the methacrylate polymer block more than 100 ℃, and B represents that glass transition temperature is the alkyl acrylate polymer blocks below-20 ℃,
(E2) content of polymer blocks B is 50～95 quality %,
(E3) weight-average molecular weight Mw is 50000～300000, and
(E4) molecular weight distribution mw/mn is 1.0～1.5.
2. pressure-sensitive adhesive for optical films as claimed in claim 1, wherein, acrylic acid series triblock copolymer (I) is to possess following condition (E1), (E2), (E3 ') and acrylic acid series triblock copolymer (Ia) (E4) and possess following condition (E1), (E2), (E3 ") and acrylic acid series triblock copolymer (Ib) (E4) with acrylic acid series triblock copolymer (Ia): the mass ratio of acrylic acid series triblock copolymer (Ib)=45: 55～75: 25 cooperates and forms
Zero acrylic acid series triblock copolymer (Ia):
(E1) the acrylic acid series triblock copolymer shown in the following general formula (1),
A1-B-A2(1)
In the formula, A1 and A2 represent independently that respectively glass transition temperature is the methacrylate polymer block more than 100 ℃, and B represents that glass transition temperature is the alkyl acrylate polymer blocks below-20 ℃,
(E2) content of polymer blocks B is 50～95 quality %,
(E3 ') weight-average molecular weight Mw is more than 50000 and less than 100000, and
(E4) molecular weight distribution mw/mn is 1.0～1.5,
Zero acrylic acid series triblock copolymer (Ib):
(E1) the acrylic acid series triblock copolymer shown in the following general formula (1),
A1-B-A2(1)
In the formula, A1 and A2 represent independently that respectively glass transition temperature is the methacrylate polymer block more than 100 ℃, and B represents that glass transition temperature is the alkyl acrylate polymer blocks below-20 ℃,
(E2) content of polymer blocks B is 50～95 quality %,
(E3 ") weight-average molecular weight Mw is 100000～300000, and
(E4) molecular weight distribution mw/mn is 1.0～1.5.
3. pressure-sensitive adhesive for optical films as claimed in claim 2, wherein, the weight-average molecular weight Mw of acrylic acid series triblock copolymer (Ib) is 100000～200000.
4. pressure-sensitive adhesive for optical films as claimed in claim 2, wherein, the content of polymer blocks B is 50～70 quality % in the acrylic acid series triblock copolymer (Ia), the content of polymer blocks B is 65～95 quality % in the acrylic acid series triblock copolymer (Ib).
5. pressure-sensitive adhesive for optical films as claimed in claim 3, wherein, the content of polymer blocks B is 50～70 quality % in the acrylic acid series triblock copolymer (Ia), the content of polymer blocks B is 65～95 quality % in the acrylic acid series triblock copolymer (Ib).
6. pressure-sensitive adhesive for optical films as claimed in claim 2, wherein, as acrylic acid series triblock copolymer (Ib), use to possess above-mentioned condition (E1), (E2) and (E4) and weight-average molecular weight Mw be more than 100000 and less than 120000 acrylic acid series triblock copolymer (Ib-1) and possess above-mentioned condition (E1), (E2) and (E4) and weight-average molecular weight Mw be 120000～200000 acrylic acid series triblock copolymer (Ib-2) with acrylic acid series triblock copolymer (Ib-1): the mass ratio of acrylic acid series triblock copolymer (Ib-2)=10: 90～90: 10 cooperates the acrylic acid series triblock copolymer that forms.
7. pressure-sensitive adhesive for optical films as claimed in claim 3, wherein, as acrylic acid series triblock copolymer (Ib), use to possess above-mentioned condition (E1), (E2) and (E4) and weight-average molecular weight Mw be more than 100000 and less than 120000 acrylic acid series triblock copolymer (Ib-1) and possess above-mentioned condition (E1), (E2) and (E4) and weight-average molecular weight Mw be 120000～200000 acrylic acid series triblock copolymer (Ib-2) with acrylic acid series triblock copolymer (Ib-1): the mass ratio of acrylic acid series triblock copolymer (Ib-2)=10: 90～90: 10 cooperates the acrylic acid series triblock copolymer that forms.
8. pressure-sensitive adhesive for optical films as claimed in claim 4, wherein, as acrylic acid series triblock copolymer (Ib), use to possess above-mentioned condition (E1), (E2) and (E4) and weight-average molecular weight Mw be more than 100000 and less than 120000 acrylic acid series triblock copolymer (Ib-1) and possess above-mentioned condition (E1), (E2) and (E4) and weight-average molecular weight Mw be 120000～200000 acrylic acid series triblock copolymer (Ib-2) with acrylic acid series triblock copolymer (Ib-1): the mass ratio of acrylic acid series triblock copolymer (Ib-2)=10: 90～90: 10 cooperates the acrylic acid series triblock copolymer that forms.
9. pressure-sensitive adhesive for optical films as claimed in claim 5, wherein, as acrylic acid series triblock copolymer (Ib), use to possess above-mentioned condition (E1), (E2) and (E4) and weight-average molecular weight Mw be more than 100000 and less than 120000 acrylic acid series triblock copolymer (Ib-1) and possess above-mentioned condition (E1), (E2) and (E4) and weight-average molecular weight Mw be 120000～200000 acrylic acid series triblock copolymer (Ib-2) with acrylic acid series triblock copolymer (Ib-1): the mass ratio of acrylic acid series triblock copolymer (Ib-2)=10: 90～90: 10 cooperates the acrylic acid series triblock copolymer that forms.
10. as any described pressure-sensitive adhesive for optical films in the claim 1～9, wherein, normality is more than 65% between above-mentioned methacrylate polymer block A1 and A2.
11. as any described pressure-sensitive adhesive for optical films in the claim 1～9, wherein, gross mass based on all solids composition that contains in the bonding agent, further contain with the ratio of 3～25 quality % possess following condition (F1), (F2), (F3) and acrylic acid series diblock copolymer (II) (F4)
Zero acrylic acid series diblock copolymer (II):
(F1) the acrylic acid series diblock copolymer shown in the following general formula (2),
C-D (2)
In the formula, C represents that methacrylate polymer block, D represent the alkyl acrylate polymer blocks,
(F2) content of polymer blocks D is 50～95 quality %,
(F3) weight-average molecular weight Mw is 50000～300000, and
(F4) molecular weight distribution mw/mn is 1.0～1.5.
12. pressure-sensitive adhesive for optical films as claimed in claim 10, wherein, based on the gross mass of all solids composition that contains in the bonding agent, further contain with the ratio of 3～25 quality % possess following condition (F1), (F2), (F3) and acrylic acid series diblock copolymer (II) (F4)
Zero acrylic acid series diblock copolymer (II):
(F1) the acrylic acid series diblock copolymer shown in the following general formula (2),
C-D (2)
In the formula, C represents that methacrylate polymer block, D represent the alkyl acrylate polymer blocks,
(F2) content of polymer blocks D is 50～95 quality %,
(F3) weight-average molecular weight Mw is 50000～300000, and
(F4) molecular weight distribution mw/mn is 1.0～1.5.
13. as any described pressure-sensitive adhesive for optical films in the claim 1～9, wherein, when measuring the dynamic viscoelastic of bonding agent under the frequency of 6.28rad/s, the energy storage elastic modulus under 23 ℃ is 1.0 * 10 5～8.0 * 10 5Pa, and the energy storage elastic modulus under 90 ℃ is 7.0 * 10 4～6.0 * 10 5Pa.
14. pressure-sensitive adhesive for optical films as claimed in claim 10, wherein, when measuring the dynamic viscoelastic of bonding agent under the frequency of 6.28rad/s, the energy storage elastic modulus under 23 ℃ is 1.0 * 10 5～8.0 * 10 5Pa, and the energy storage elastic modulus under 90 ℃ is 7.0 * 10 4～6.0 * 10 5Pa.
15. pressure-sensitive adhesive for optical films as claimed in claim 11, wherein, when measuring the dynamic viscoelastic of bonding agent under the frequency of 6.28rad/s, the energy storage elastic modulus under 23 ℃ is 1.0 * 10 5～8.0 * 10 5Pa, and the energy storage elastic modulus under 90 ℃ is 7.0 * 10 4～6.0 * 10 5Pa.
16. pressure-sensitive adhesive for optical films as claimed in claim 12, wherein, when measuring the dynamic viscoelastic of bonding agent under the frequency of 6.28rad/s, the energy storage elastic modulus under 23 ℃ is 1.0 * 10 5～8.0 * 10 5Pa, and the energy storage elastic modulus under 90 ℃ is 7.0 * 10 4～6.0 * 10 5Pa.
17. as any described pressure-sensitive adhesive for optical films in the claim 1～9, it is the solvent-based adhesive that is dissolved in the organic solvent.
18. as any described pressure-sensitive adhesive for optical films in the claim 1～9, wherein, make the toluene solution that solid component concentration is 45 quality %, the solution viscosity of measuring with Brookfield viscometer under 25 ℃ temperature is 1000～4000mPas.
19. adhesive optical film or adhesive optical film diaphragm, it has by any bonding coat that described pressure-sensitive adhesive for optical films forms in the claim 1～18, forms without the cross-linking step manufacturing.
20. image display device wherein uses described adhesive optical film of claim 19 and/or adhesive optical film diaphragm.
CN2007800444867A 2006-12-01 2007-11-26 Pressure-sensitive adhesive for optical films Active CN101548204B (en)

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